Herbicidal quinoline and 1,8 -naphthyridine compounds

ABSTRACT

The present invention relates to novel herbicidal oxopyridine and thionopyridine derivatives of Formula (I), or an agronomically acceptable salt of said compound wherein R 1 , R 5 , R 6 , R 7 , X 1 , X 2  and Q are as defined herein. The invention further relates to processes and intermediates for the preparation of the oxopyridine derivatives, to compositions which comprise the herbicidal compounds, and to their use for controlling weeds, in particular in crops of useful plants.

The present invention relates to novel herbicidal oxopyridine andthionopyridine derivatives, to processes for their preparation, tocompositions which comprise the herbicidal compounds, and to their usefor controlling weeds, in particular in crops of useful plants, or forinhibiting plant growth.

According to the present invention there is provided a herbicidalcompound of Formula (I):

or an agronomically acceptable salt of said compound, wherein:

-   R¹ is selected from the group consisting of hydrogen, C₁-C₆alkyl,    C₁-C₆haloalkyl, C₁-C₃alkoxy-C₁-C₃ alkyl,    C₁-C₃alkoxy-C₁-C₃alkoxy-C₁-C₃-alkyl, C₁-C₃alkoxy-C₁-C₃-haloalkyl,    C₁-C₃-alkoxy-C₁-C₃-alkoxy-C₁-C₃-haloalkyl, C₄-C₆ -oxasubstituted    cycloalkoxy-C₁-C₃ -alkyl, C₄-C₆-oxasubstituted    cycloalkyl-C₁-C₃-alkoxy-C₁-C₃-alkyl, C₄-C₆-oxasubstituted    cycloalkoxy-C₁-C₃-haloalkyl, C₄-C₆-oxasubstituted    cycloalkyl-C₁-C₃-alkoxy-C₁-C₃-haloalkyl, (C₁-C₃ alkanesulfonyl-C₁-C₃    alkylamino)-C₁-C₃ alkyl,    (C₁-C₃alkanesulfonyl-C₃-C₄cycloalkylamino)-C₁-C₃alkyl,    C₁-C₆alkylcarbonyl-C₁-C₃alkyl, C₃-C₆cycloalkyl-C₂-C₆alkenyl,    C₃-C₆alkynyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, cyano-C₁-C₆-alkyl,    arylcarbonyl-C₁-C₃-alkyl (wherein the aryl may be optionally    substituted with one or more substituents from the group consisting    of halo, C₁-C₃-alkoxy, C₁-C₃-alkyl, C₁-C₃ haloalkyl),    aryl-C₁-C₆alkyl, aryloxy-C₁-C₆alkyl (wherein both cases the aryl may    be optionally substituted with one or more substituents from the    group consisting of halo, C₁-C₃-alkoxy, C₁-C₃-alkyl, C₁-C₃    haloalkyl), and a three- to ten-membered mono- or bicyclic ring    system, which may be aromatic, saturated or partially saturated and    can contain from 1 to 4 heteroatoms each independently selected from    the group consisting of nitrogen, oxygen and sulphur the ring system    being optionally substituted by one or more substituents selected    from the group consisting of C₁-C₃alkyl, C₁-C₃haloalkyl,    C₁-C₃alkenyl, C₁-C₃alkynyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy,    C₁-C₆alkyl-S(O)p-, C₁-C₆haloalkyl-S(O)p-, aryl, aryl-S(O)p,    heteroaryl-S(O)p, aryloxy, heteroaryloxy, C₁-C₃ alkoxycarbonyl,    C₁-C₃ alkylamino-S(O)p-, C₁-C₃ alkylamino-S(O)p-C₁-C₃ alkyl, C₁-C₃    dialkylamino-S(O)p-, C₁-C₃ dialkylamino-S(O)p-C₁-C₃ alkyl, C₁-C₃    alkylaminocarbonyl-, C₁-C₃ alkylaminocarbonyl-C₁-C₃ alkyl, C₁-C₃    dialkylaminocarbonyl, C₁-C₃ dialkylaminocarbonyl-C₁-C₃ alkyl, C₁-C₃    alkylcarbonylamino, C₁-C₃ alkyl-S(O)p-amino, cyano and nitro; the    heteroaryl substituents containing one to three heteroatoms each    independently selected from the group consisting of oxygen, nitrogen    and sulphur, and wherein the aryl or heteroaryl component may be    optionally substituted by one or more substituents selected from the    group consisting of halo, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃ alkoxy,    C₁-C₃ haloalkoxy, phenyl, cyano and nitro;

R⁵ is selected from the group consisting of hydrogen, chloro, fluoro andmethyl;

R⁶ is selected from the group consisting of hydrogen, fluorine,chlorine, hydroxyl and methyl;

R⁷ is selected from the group consisting of hydrogen, cyano, nitro,halogen, hydroxyl, sulfhydryl, C₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆alkenyl, aryl-C₂-C₆alkenyl,C₃-C₆alkynyl, C₁-C₆alkoxy, C₄-C₇ cycloalkoxy, C₁-C₆haloalkoxy,C₁-C₆alkyl-S(O)p, C₃-C₆cycloalkyl-S(O)p C₁-C₆haloalkyl-S(O)p, C₃-C₆halocycloalkyl-S(O)p, C₁-C₆alkylcarbonylamino,(C₁-C₆alkylcarbonyl)C₁-C₃alkylamino, (C₃-C₆cycloalkylcarbonyl)amino,(C₃-C₆cycloalkylcarbonyl)C₁-C₃alkylamino, arylcarbonylamino,(arylcarbonyl)-C₁-₃alkylamino, (heteroarylcarbonyl)amino,(heteroarylcarbonyl)C₁-C₃alkylamino, amino, C₁-C₆alkylamino,C₂-C₆dialkylamino, C₂-C₆alkenylamino, C₁-C₆alkoxy-C₂-C₆-alkylamino,(C₁-C₆alkoxy-C₂-C₄-alkyl)-C₁-C₆-alkylamino, C₃-C₆ cycloalkylamino, C₃-C₆cyclohaloalkylamino, C₁-C₃alkoxy-C₃-C₆cycloalkylamino, C₃-C₆alkynylamino, dialkylamino in which the substituents join to form a 4-6membered ring (e.g pyrrolidinyl, piperidinyl) optionally containingoxygen (e.g morpholinyl) and/or optionally substituted by C₁-C₃-alkoxyand/or halogen (especially fluorine), C₂-C₆dialkylaminosulfonyl,C₁-C₆alkylaminosulfonyl, C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆alkoxy-C₂-C₆alkoxy, C₁-C₆alkoxy-C₂-C₆alkoxy-C₁-C₆-alkyl,C₃-C₆alkenyl-C₂-C₆alkoxy, C₃-C₆alkynyl-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl,C₁-C₆alkylcarbonyl, C₁-C₄alkylenyl-S(O)p-R′, C₁-C₄alkylenyl-CO₂-R′,C₁-C₄alkylenyl-(CO)N-R′R′, aryl (e.g. phenyl), aryl C₁-C₃alkyl,aryl-S(O)p, heteroaryl-S(O)p, aryloxy (e.g phenoxy), a 5 or 6-memberedheteroaryl, heteroaryl C₁-C₃ alkyl and heteroaryloxy, the heteroarylcontaining one to three heteroatoms, each independently selected fromthe group consisting of oxygen, nitrogen and sulphur, wherein the arylor heteroaryl component may be optionally substituted by one or moresubstituents selected from the group consisting of C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃ alkoxy, C₁-C₃haloalkoxy, halo, cyano and nitro;

-   X¹═N—(O)n or C—R⁸;-   X²═O or S;-   n=0 or 1;-   p=0, 1 or 2;-   R′ is independently selected from the group consisting of hydrogen    and C₁-C₆alkyl;-   R⁸ is selected from the group consisting of hydrogen, halogen,    C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkylcarbonyl-C₁-C₃alkyl,    C₃-C₆cycloalkyl-C₂-C₆alkenyl for example cyclohexylmethylenyl,    C₃-C₆alkynyl (for example propargyl), C₂-C₆-alkenyl (for example    allyl), C₁-C₆alkoxy C₁-C₆alkyl, cyano-C₁-C₆-alkyl,    arylcarbonyl-C₁-C₃-alkyl (wherein the aryl may be optionally    substituted with one or more substituents selected from the group    consisting of halo, C₁-C₃-alkoxy, C₁-C₃-alkyl, C₁-C₃ haloalkyl),    aryl-C₁-C₆alkyl (wherein the aryl may be optionally substituted with    one or more substituents from the group consisting of halo,    C₁-C₃-alkoxy, C₁-C₃-alkyl, C₁-C₃ haloalkyl), C₁-C₆alkoxyC₁-C₆alkoxy    C₁-C₆alkyl, aryl, a 5 or 6-membered heteroaryl, a 5 or 6-membered    heteroaryl-C₁-C₃-alkyl and heterocyclyl-C₁-C₃-alkyl, the heteroaryl    or heterocyclyl containing one to three heteroatoms each    independently selected from the group consisting of oxygen, nitrogen    and sulphur, and wherein the aryl, heterocyclyl or heteroaryl    component may be optionally substituted by one or more substituents    from the group consisting of halogen, C₁-C₃alkyl, C₁-C₃haloalkyl and    C₁-C₃ alkoxy, cyano and nitro;-   Q is selected from the group consisting of:—

wherein

-   A¹ is selected from the group consisting of O, C(O), S, SO, SO₂ and    (CR^(e)R^(f))_(q);-   q=0, 1 or 2;-   R^(a), R^(b), R^(c), R^(d), R^(e) and R^(f) are each independently    selected from the group consisting of C₁-C₄alkyl which may be mono-,    di- or tri-substituted by substituents selected from the group    consisting of C₁-C₄alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl,    C₁-C₄alkoxycarbonyl, C₁-C₄alkylthio, C₁-C₄alkylsulfonyl,    C₁-C₄alkylcarbonyl, phenyl and heteroaryl, it being possible for the    phenyl and heteroaryl groups in turn to be mono-, di- or    tri-substituted by substituents selected from the group consisting    of C₁-C₄alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl,    C₁-C₄alkoxycarbonyl, C₁-C₄alkylsulfonyl and C₁-C₄haloalkyl, the    substituents on the nitrogen in the heterocyclic ring being other    than halogen; or-   R^(a), R^(b), R^(e), R^(d), R^(e) and R^(f) are each independently    selected from the group consisting of hydrogen, C₁-C₄alkoxy,    halogen, hydroxy, cyano, hydroxycarbonyl, C₁-C₄alkoxycarbonyl,    C₁-C₄alkylthio, C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl,    C₁-C₄alkylcarbonyl, phenyl or heteroaryl, it being possible for the    phenyl and heteroaryl groups in turn to be mono-, di- or    tri-substituted by substituents selected from the group consisting    of C₁-C₄alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl,    C₁-C₄alkoxycarbonyl, C₁-C₄alkylsulfonyl and C₁-C₄haloalkyl, the    substituents on the nitrogen in the heterocyclic ring being other    than halogen; or-   R^(a) and R^(b) together form a 3- to 5-membered carbocyclic ring    which may be substituted by C₁-C₄alkyl and may be interrupted by    oxygen, sulfur, S(O), SO₂, OC(O), NR^(g) or by C(O); or-   R^(a) and R^(c) together form a C₁-C₃alkylene chain which may be    interrupted by oxygen, sulfur, SO, SO₂, OC(O), Me or by C(O); it    being possible for that C₁-C₃alkylene chain in turn to be    substituted by C₁-C₄alkyl;-   R^(g) and R^(h) are each independently of the other C₁-C₄alkyl,    C₁-C₄haloalkyl, C₁-C₄alkylsulfonyl, C₁-C₄alkylcarbonyl or    C₁-C₄alkoxycarbonyl;-   R^(i) is C₁-C₄alkyl;-   R^(j) is selected from the group consisting of hydrogen, C₁-C₄ alkyl    and C₃-C₆ cycloalkyl;-   R³ is selected from the group consisting of C₁-C₆alkyl, optionally    substituted with halogen and/or C₁-C₃alkoxy, and C₃-C₆ cycloalkyl    optionally substituted with halogen and/or C₁-C₃alkoxy;-   R⁹ is selected from the group consisting of cyclopropyl, CF₃ and    i.-Pr;-   R¹⁰ is selected from the group consisting of hydrogen, I, Br, SR¹¹,    S(O)R¹¹, S(O)₂R¹¹ and CO₂R¹¹; and-   R¹¹ is C₁₋₄ alkyl.

Halogen encompasses fluorine, chlorine, bromine or iodine. The samecorrespondingly applies to halogen in the context of other definitions,such as haloalkyl or halophenyl.

Haloalkyl groups having a chain length of from 1 to 6 carbon atoms are,for example, fluoromethyl, difluoromethyl, trifluoromethyl,chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl,2-fluoroethyl, 2-chloroethyl, pentafluoroethyl,1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and2,2,2-trichloroethyl, heptafluoro-n-propyl and perfluoro-n-hexyl.

Suitable alkylenyl radicals include, for example CH₂, CHCH₃, C(CH₃)₂,CH₂CHCH₃, CH₂CH(C₂H₅).

Suitable haloalkenyl radicals include alkenyl groups substituted one ormore times by halogen, halogen being fluorine, chlorine, bromine oriodine and especially fluorine or chlorine, for example2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl,3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and4,4,4-trifluorobut-2-en-1-yl. Preferred C₂-C₆alkenyl radicalssubstituted once, twice or three times by halogen are those having achain length of from 2 to 5 carbon atoms. Suitable haloalkylalkynylradicals include, for example, alkylalkynyl groups substituted one ormore times by halogen, halogen being bromine or iodine and, especially,fluorine or chlorine, for example 3-fluoropropynyl,5-chloropent-2-yn-1-yl, 5-bromopent-2-yn-l-yl, 3,3,3-trifluoropropynyland 4,4,4-trifluoro-but-2-yn-l-yl. Preferred alkylalkynyl groupssubstituted one or more times by halogen are those having a chain lengthof from 3 to 5 carbon atoms.

Alkoxy groups preferably have a chain length of from 1 to 6 carbonatoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy,n-butoxy, isobutoxy, sec-butoxy or tert-butoxy or a pentyloxy orhexyloxy isomer, preferably methoxy and ethoxy. Alkylcarbonyl ispreferably acetyl or propionyl. Alkoxycarbonyl is, for example,methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl,n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl ortert-butoxycarbonyl, preferably methoxycarbonyl, ethoxycarbonyl ortert-butoxycarbonyl.

Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy,trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy,2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy or2,2,2-trichloroethoxy, preferably difluoromethoxy, 2-chloroethoxy ortrifluoromethoxy.

Alkylthio groups preferably have a chain length of from 1 to 6 carbonatoms. Alkylthio is, for example, methylthio, ethylthio, propylthio,isopropylthio, n-butylthio, isobutylthio, sec-butylthio ortert-butylthio, preferably methylthio or ethylthio. Alkylsulfinyl is,for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl,isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinylor tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.

Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl,propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl,sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl orethylsulfonyl.

Alkylamino is, for example, methylamino, ethylamino, n-propylamino,isopropylamino or a butylamino isomer. Dialkylamino is, for example,dimethylamino, methylethylamino, diethylamino, n-propylmethylamino,dibutylamino or diisopropylamino. Preference is given to alkylaminogroups having a chain length of from 1 to 4 carbon atoms.

Cycloalkylamino or dicycloalkylamino is for example cyclohexylamino ordicyclopropylamino.

Alkoxyalkyl groups preferably have from 1 to 6 carbon atoms. Alkoxyalkylis, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl,n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.

Alkylthioalkyl groups preferably have from 1 to 6 carbon atoms.Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl,ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl,isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethylor butylthiobutyl.

Three- to ten-membered mono- or bicyclic ring system may be aromatic,saturated or partially saturated and can contain from 1 to 4 heteroatomseach independently selected from the group consisting of nitrogen,oxygen and sulphur the ring system being optionally substituted by oneor more substituents independently selected from the group consisting ofC₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkenyl, C₁-C₃alkynyl, C₁-C₃ alkoxy,C₁-C₃ haloalkoxy, C₁-C₆alkyl-S(O)p-, C₁-C₆haloalkyl-S(O)p-, aryl,aryl-S(O)p, heteroaryl-S(O)p, aryloxy, heteroaryloxy, C₁-C₃alkoxycarbonyl, C₁-C₃ alkylamino-S(O)p-, C₁-C₃ alkylamino-S(O)p-C₁-C₃alkyl, C₁-C₃ dialkylamino-S(O)p-, C₁-C₃ dialkylamino-S(O)p-C₁-C₃ alkyl,C₁-C₃ alkylaminocarbonyl-, C₁-C₃ alkylaminocarbonyl-C₁-C₃ alkyl, C₁-C₃dialkylaminocarbonyl, C₁-C₃ dialkylaminocarbonyl-C₁-C₃ alkyl, C₁-C₃alkylcarbonylamino, C₁-C₃ alkyl-S(O)p-amino, cyano and nitro. Such ringsystems thus include, for example, cycloalkyl, phenyl, heterocyclyl andheteroaryl. Examples of “partially saturated” rings include, forexample, 1,4 benzodioxin and 1,3 benzodioxole.

Cycloalkyl groups preferably have from 3 to 6 ring carbon atoms and maybe substituted by one or more methyl groups; they are preferablyunsubstituted, for example cyclopropyl, cyclobutyl, cyclopentyl orcyclohexyl.

Aryl includes benzyl, phenyl, including phenyl as part of a substituentsuch as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl,phenoxyalkyl or tosyl, may be in mono- or poly-substituted form, inwhich case the substituents may, as desired, be in the ortho-, meta-and/or para-position(s).

Heterocyclyl, for example, includes morpholinyl, tetrahydrofuryl.

Heteroaryl, including heteroaryl as part of a substituent such asheteroaryloxy, means, for example, a five or six member heteroarylcontaining one to three heteroatoms, each independently selected fromthe group consisting of oxygen, nitrogen and sulphur. It should beunderstood that the heteroaryl component may be optionally mono or polysubstituted. The term heteroaryl thus includes, for example, furanyl,thiophenyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyrazolyl,isothiazolyl, pyridyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazolyl.

Compounds of Formula I may contain asymmetric centres and may be presentas a single enantiomer, pairs of enantiomers in any proportion or, wheremore than one asymmetric centre are present, contain diastereoisomers inall possible ratios. Typically one of the enantiomers has enhancedbiological activity compared to the other possibilities.

Similarly, where there are disubstituted alkenes, these may be presentin E or Z form or as mixtures of both in any proportion.

Furthermore, compounds of Formula I comprising Q1, Q5, Q6 or Q7 or whenR¹ is hydrogen may be in equilibrium with alternative hydroxyltautomeric forms. It should be appreciated that all tautomeric forms(single tautomer or mixtures thereof), racemic mixtures and singleisomers are included within the scope of the present invention.

The skilled person will also appreciate that if n is 1 with regard toFormula I to form the N-oxide then the nitrogen and oxygen will becharged accordingly (N⁺O⁻).

In a preferred embodiment of the present invention X² is oxygen.

In another preferred embodiment R¹ is selected from the group consistingof hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₃alkoxyC₁-C₃alkyl,C₁-C₃alkoxy C₂-C₃alkoxyC₁-C₃alkyl, C₁-C₆haloalkyl, C₂-C₆haloalkenylC₁-C₃alkoxy-C₁-C₃haloalkyl and phenyl.

In another preferred embodiment R¹ is aryl, preferably phenyl, or a 5 or6-membered heteroaryl containing one to three heteroatoms eachindependently selected from the group consisting of oxygen, nitrogen andsulphur, and wherein the aryl or heteroaryl may be optionallysubstituted by one or more substituents selected from the groupconsisting of halo, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃ alkoxy, C₁-C₃haloalkoxy, C₁-C₆alkyl-S(O)p-, C₁-C₆haloalkyl-S(O)p-, cyano and nitro.Especially preferred is wherein R¹ is an optionally substituted arylselected from the group consisting of phenyl, phenoxy,phenoxy-C₁-C₆alkyl, benzyl, thiophenyl, 1,4 benzodioxinyl, 1,3benzodioxoleyl and pyridyl.

In another preferred embodiment R⁵ is hydrogen or methyl.

In another preferred embodiment R⁶ is hydrogen or fluorine.

In another preferred embodiment R³ is selected from the group consistingof hydrogen, methyl and cyclopropyl.

In another preferred embodiment the herbicidal compound is of Formula(Ia):

In a more preferred embodiment of the present invention the herbicidalcompound is of Formula (Ia) wherein Q is Q1, in particular wherein A^(l)is CR^(e)R^(f) and wherein R^(a), R^(b), R^(c), R^(d), R^(e) and R^(f)are hydrogen, and wherein q=1. In another preferred embodiment of thepresent invention Q is Q1, wherein A^(l) is CR^(e)R^(f) and wherein,R^(b), R^(d), R^(e) and R^(f) are hydrogen, R^(a) and R^(e) togetherform an ethylene chain and wherein q=1

In another preferred embodiment, when the herbicidal compound is ofFormula (Ia) and wherein R⁷ is selected from the group consisting ofhydrogen, hydroxyl, halogen, C₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆haloalkyl, C₁-C₆ alkoxy, C₁-C₆ alkoxy-C₂-C₆-alkoxy,C₁-C₆-alkoxy-C₁-C₆ alkyl, C₁-C₆-alkoxy-C₂-C₆-alkoxy-C₁-C₆ alkyl,C₁-C₆alkylamino, C₁-C₆dialkylamino, C₂-C₆alkenylamino,C₁-C₆alkoxy-C₂-C₃-alkylamino,(C₁-C₆alkoxy-C₂-C₄-alkyl)-C₁-C₆-alkylamino, C₃-C₆ cycloalkylamino, C₃-C₆cyclohaloalkylamino, C₁-C₃alkoxy-C₃-C₆ cycloalkylamino, C₃-C₆alkynylamino and dialkylamino group in which the substituents join toform a 4-6 membered ring, optionally containing oxygen, and/oroptionally substituted by C₁-C₃-alkoxy and/or halogen, especiallyfluorine, In an even more preferred embodiment R⁷ is selected from thegroup consisting of hydrogen, fluoro, bromo, chloro, methyl, ethyl,1-methylethyl, cyclopropyl, fluoromethyl, 1-fluoroethyl,1,1-difluoroethyl, 2,2-difluoroethyl, 1-fluoro-1-methylethyl,2,2,2-trifluoroethyl, difluorochloromethyl, methoxy, ethoxy,methoxymethyl, 1-methoxyethyl, 2-methoxyethoxy, 2-methoxyethoxymethyl,(2-methoxyethyl)amino and (2-methoxyethyl)methylamino. Hydrogen andmethyl are particularly preferred.

In another preferred embodiment the herbicidal compound is of Formula(Ib):

In another preferred embodiment of the present invention the herbicidalcompound is of Formula (Ib), wherein Q is Q1, in particular wherein A¹is CR^(e)R^(f) and wherein R^(a), R^(b), R^(e), R^(d), R^(e) and Warehydrogen, and wherein q=1. In another preferred embodiment of thepresent invention Q is Q1, wherein A^(l) is CR^(e)R^(f) and wherein, le,R^(d), R^(e) and R^(f) are hydrogen, R^(a) and R^(e) together form anethylene chain and wherein q=1.

In another preferred embodiment wherein the herbicidal compound is ofFormula (Ib) and wherein R⁷ is selected from the group consisting ofhydrogen, cyano, halogen, nitro, C₁-C₆haloalkyl, C₁-C₃ alkoxyC₁-C₃haloalkyl, C₁-C₃ alkoxyC₂-C₆-alkoxyC₁-C₃haloalkyl, C₁-C₆haloalkoxy,C₁-C₆alkylS(O)p,C₃-₆cycloalkylS(O)p C₁ -C₆haloalkyl-S(O)p,C₃-C₆halocycloalkyl-S(O)p, aryl-S(O)p and heteroaryl-S(O)p. In an evenmore preferred embodiment R⁷ is selected from the group consisting ofchloro, fluoro, cyano, nitro, fluoromethyl, difluoromethyl,trifluoromethyl, 1-fluoroethyl, 1,1-difluoroethyl,1-fluoro-1-methylethyl, difluorochloromethyl, difluoromethoxy,trifluoromethoxy, 1,1-difluoroethoxy, methylsulfinyl, methylsulfonyl,ethylsulfinyl, ethylsulfonyl, phenyl sulfinyl and phenyl sulfonyl.

The present invention also includes agronomically acceptable salts thatthe compounds of Formula I may form with amines (for example ammonia,dimethylamine and triethylamine), alkali metal and alkaline earth metalbases or quaternary ammonium bases. Among the alkali metal and alkalineearth metal hydroxides, oxides, alkoxides and hydrogen carbonates andcarbonates used as salt formers, emphasis is to be given to thehydroxides, alkoxides, oxides and carbonates of lithium, sodium,potassium, magnesium and calcium, but especially those of sodium,magnesium and calcium. The corresponding trimethylsulfonium salt mayalso be used.

The compounds of Formula (I) according to the invention can be used asherbicides by themselves, but they are generally formulated intoherbicidal compositions using formulation adjuvants, such as carriers,solvents and surface-active agents (SFAs). Thus, the present inventionfurther provides a herbicidal composition comprising a herbicidalcompound according to any one of the previous claims and anagriculturally acceptable formulation adjuvant. The composition can bein the form of concentrates which are diluted prior to use, althoughready-to-use compositions can also be made. The final dilution isusually made with water, but can be made instead of, or in addition to,water, with, for example, liquid fertilisers, micronutrients, biologicalorganisms, oil or solvents.

The herbicidal compositions generally comprise from 0.1 to 99% byweight, especially from 0.1 to 95% by weight, compounds of Formula I andfrom 1 to 99.9% by weight of a formulation adjuvant which preferablyincludes from 0 to 25% by weight of a surface-active substance.

The compositions can be chosen from a number of formulation types, manyof which are known from the Manual on Development and Use of FAOSpecifications for Plant Protection Products, 5th Edition, 1999. Theseinclude dustable powders (DP), soluble powders (SP), water solublegranules (SG), water dispersible granules (WG), wettable powders (WP),granules (GR) (slow or fast release), soluble concentrates (SL), oilmiscible liquids (OL), ultra low volume liquids (UL), emulsifiableconcentrates (EC), dispersible concentrates (DC), emulsions (both oil inwater (EW) and water in oil (EO)), micro-emulsions (ME), suspensionconcentrates (SC), aerosols, capsule suspensions (CS) and seed treatmentformulations. The formulation type chosen in any instance will dependupon the particular purpose envisaged and the physical, chemical andbiological properties of the compound of Formula (I).

Dustable powders (DP) may be prepared by mixing a compound of Formula(I) with one or more solid diluents (for example natural clays, kaolin,pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk,diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulphur, lime, flours, talc and other organic and inorganicsolid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a compound of Formula (I)with one or more water-soluble inorganic salts (such as sodiumbicarbonate, sodium carbonate or magnesium sulphate) or one or morewater-soluble organic solids (such as a polysaccharide) and, optionally,one or more wetting agents, one or more dispersing agents or a mixtureof said agents to improve water dispersibility/solubility. The mixtureis then ground to a fine powder. Similar compositions may also begranulated to form water soluble granules (SG).

Wettable powders (WP) may be prepared by mixing a compound of Formula(I) with one or more solid diluents or carriers, one or more wettingagents and, preferably, one or more dispersing agents and, optionally,one or more suspending agents to facilitate the dispersion in liquids.The mixture is then ground to a fine powder. Similar compositions mayalso be granulated to form water dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of acompound of Formula (I) and one or more powdered solid diluents orcarriers, or from pre-formed blank granules by absorbing a compound ofFormula (I) (or a solution thereof, in a suitable agent) in a porousgranular material (such as pumice, attapulgite clays, fuller's earth,kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing acompound of Formula (I) (or a solution thereof, in a suitable agent) onto a hard core material (such as sands, silicates, mineral carbonates,sulphates or phosphates) and drying if necessary. Agents which arecommonly used to aid absorption or adsorption include solvents (such asaliphatic and aromatic petroleum solvents, alcohols, ethers, ketones andesters) and sticking agents (such as polyvinyl acetates, polyvinylalcohols, dextrins, sugars and vegetable oils). One or more otheradditives may also be included in granules (for example an emulsifyingagent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compoundof Formula (I) in water or an organic solvent, such as a ketone, alcoholor glycol ether. These solutions may contain a surface active agent (forexample to improve water dilution or prevent crystallisation in a spraytank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may beprepared by dissolving a compound of Formula (I) in an organic solvent(optionally containing one or more wetting agents, one or moreemulsifying agents or a mixture of said agents). Suitable organicsolvents for use in ECs include aromatic hydrocarbons (such asalkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100,SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark),ketones (such as cyclohexanone or methylcyclohexanone) and alcohols(such as benzyl alcohol, furfuryl alcohol or butanol),N-allcylpyrrolidones (such as N-methylpyrrolidone orN-octylpyrrolidone), dimethyl amides of fatty acids (such as C₈-C₁₀fatty acid dimethylamide) and chlorinated hydrocarbons. An EC productmay spontaneously emulsify on addition to water, to produce an emulsionwith sufficient stability to allow spray application through appropriateequipment.

Preparation of an EW involves obtaining a compound of Formula (I) eitheras a liquid (if it is not a liquid at room temperature, it may be meltedat a reasonable temperature, typically below 70° C.) or in solution (bydissolving it in an appropriate solvent) and then emulsifying theresultant liquid or solution into water containing one or more SFAs,under high shear, to produce an emulsion. Suitable solvents for use inEWs include vegetable oils, chlorinated hydrocarbons (such aschlorobenzenes), aromatic solvents (such as alkylbenzenes oralkylnaphthalenes) and other appropriate organic solvents which have alow solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend of oneor more solvents with one or more SFAs, to produce spontaneously athermodynamically stable isotropic liquid formulation. A compound ofFormula (I) is present initially in either the water or the solvent/SFAblend. Suitable solvents for use in MEs include those hereinbeforedescribed for use in in ECs or in EWs. An ME may be either anoil-in-water or a water-in-oil system (which system is present may bedetermined by conductivity measurements) and may be suitable for mixingwater-soluble and oil-soluble pesticides in the same formulation. An MEis suitable for dilution into water, either remaining as a microemulsionor forming a conventional oil-in-water emulsion.

Suspension concentrates (SC) may comprise aqueous or non-aqueoussuspensions of finely divided insoluble solid particles of a compound ofFormula (I). SCs may be prepared by ball or bead milling the solidcompound of Formula (I) in a suitable medium, optionally with one ormore dispersing agents, to produce a fine particle suspension of thecompound. One or more wetting agents may be included in the compositionand a suspending agent may be included to reduce the rate at which theparticles settle. Alternatively, a compound of Formula (I) may be drymilled and added to water, containing agents hereinbefore described, toproduce the desired end product.

Aerosol formulations comprise a compound of Formula (I) and a suitablepropellant (for example n-butane). A compound of Formula (I) may also bedissolved or dispersed in a suitable medium (for example water or awater miscible liquid, such as n-propanol) to provide compositions foruse in non-pressurised, hand-actuated spray pumps.

Capsule suspensions (CS) may be prepared in a manner similar to thepreparation of EW formulations but with an additional polymerisationstage such that an aqueous dispersion of oil droplets is obtained, inwhich each oil droplet is encapsulated by a polymeric shell and containsa compound of Formula (I) and, optionally, a carrier or diluenttherefor. The polymeric shell may be produced by either an interfacialpolycondensation reaction or by a coacervation procedure. Thecompositions may provide for controlled release of the compound ofFormula (I) and they may be used for seed treatment. A compound ofFormula (I) may also be formulated in a biodegradable polymeric matrixto provide a slow, controlled release of the compound.

The composition may include one or more additives to improve thebiological performance of the composition, for example by improvingwetting, retention or distribution on surfaces; resistance to rain ontreated surfaces; or uptake or mobility of a compound of Formula (I).Such additives include surface active agents (SFAs), spray additivesbased on oils, for example certain mineral oils or natural plant oils(such as soy bean and rape seed oil), and blends of these with otherbio-enhancing adjuvants (ingredients which may aid or modify the actionof a compound of Formula (I)).

Wetting agents, dispersing agents and emulsifying agents may be SFAs ofthe cationic, anionic, amphoteric or non-ionic type.

Suitable SFAs of the cationic type include quaternary ammonium compounds(for example cetyltrimethyl ammonium bromide), imidazolines and aminesalts.

Suitable anionic SFAs include alkali metals salts of fatty acids, saltsof aliphatic monoesters of sulphuric acid (for example sodium laurylsulphate), salts of sulphonated aromatic compounds (for example sodiumdodecylbenzenesulphonate, calcium dodecylbenzenesulphonate,butylnaphthalene sulphonate and mixtures of sodium di-isopropyl- andtri-isopropyl-naphthalene sulphonates), ether sulphates, alcohol ethersulphates (for example sodium laureth-3-sulphate), ether carboxylates(for example sodium laureth-3-carboxylate), phosphate esters (productsfrom the reaction between one or more fatty alcohols and phosphoric acid(predominately mono-esters) or phosphorus pentoxide (predominatelydi-esters), for example the reaction between lauryl alcohol andtetraphosphoric acid; additionally these products may be ethoxylated),sulphosuccinamates, paraffin or olefine sulphonates, taurates andlignosulphonates.

Suitable SFAs of the amphoteric type include betaines, propionates andglycinates.

Suitable SFAs of the non-ionic type include condensation products ofalkylene oxides, such as ethylene oxide, propylene oxide, butylene oxideor mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetylalcohol) or with alkylphenols (such as octylphenol, nonyiphenol oroctylcresol); partial esters derived from long chain fatty acids orhexitol anhydrides; condensation products of said partial esters withethylene oxide; block polymers (comprising ethylene oxide and propyleneoxide); alkanolamides; simple esters (for example fatty acidpolyethylene glycol esters); amine oxides (for example lauryl dimethylamine oxide); and lecithins.

Suitable suspending agents include hydrophilic colloids (such aspolysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose)and swelling clays (such as bentonite or attapulgite).

The composition of the present may further comprise at least oneadditional pesticide. For example, the compounds according to theinvention can also be used in combination with other herbicides or plantgrowth regulators. In a preferred embodiment the additional pesticide isa herbicide and/or herbicide safener. Examples of such mixtures are (inwhich ‘I’ represents a compound of Formula I). I+acetochlor,I+acifluorfen, I+acifluorfen-sodium, I+aclonifen, I+acrolein,I+alachlor, I+alloxydim, I+ametryn, I+amicarbazone, I+amidosulfuron,I+aminopyralid, I+amitrole, I+anilofos, I+asulam, I+atrazine,I+azafenidin, I+azimsulfuron, I+

BCPC, I+beflubutamid, I+benazolin, I+bencarbazone, I+benfluralin,I+benfuresate, I+bensulfuron, I+bensulfuron-methyl, I+bensulide,I+bentazone, I+benzfendizone, I+benzobicyclon, I+benzofenap, I+bifenox,I+bilanafos, I+bispyribac, I+bispyribac-sodium, I+borax, I+bromacil,I+bromobutide, I+bromoxynil, I+butachlor, I+butamifos, I+butralin,I+butroxydim, I+butylate, I+cacodylic acid, I+calcium chlorate,I+cafenstrole, I+carbetamide, I+carfentrazone, I+carfentrazone-ethyl,I+chlorflurenol, I+chlorflurenol-methyl, I+chloridazon, I+chlorimuron,I+chlorimuron-ethyl, I+chloroacetic acid, I+chlorotoluron,I+chlorpropham, I+chlorsulfuron, I+chlorthal, I+chlorthal-dimethyl,I+cinidon-ethyl, I+cinmethylin, I+cinosulfuron, I+cisanilide,I+clethodim, I+clodinafop, I+clodinafop-propargyl, I+clomazone,I+clomeprop, I+clopyralid, I+cloransulam, I+cloransulam-methyl,I+cyanazine, I+cycloate, I+cyclosulfamuron, I+cycloxydim, I+cyhalofop,I+cyhalofop-butyl, I+2,4-D, I+daimuron, I+dalapon, I+dazomet, I+2,4-DB,I+I+desmedipham, I+dicamba, I+dichlobenil, I+dichlorprop,I+dichlorprop-P, I+diclofop, I+diclofop-methyl, I+diclosulam,I+difenzoquat, I+difenzoquat metilsulfate, I+diflufenican,I+diflufenzopyr, I+dimefuron, I+dimepiperate, I+dimethachlor,I+dimethametryn, I+dimethenamid, I+dimethenamid-P, I+dimethipin,I+dimethylarsinic acid, T+dinitramine, I+dinoterb, I+diphenamid,I+dipropetryn, I+diquat, I+diquat dibromide, I+dithiopyr, I+diuron,I+endothal, I+EPTC, I+esprocarb, I+ethalfluralin, I+ethametsulfuron,I+ethametsulfuron-methyl, I+ethephon, I+ethofumesate, I+ethoxyfen,I+ethoxysulfuron, I+etobenzanid, I+fenoxaprop-P, I+fenoxaprop-P-ethyl,I+fentrazamide, I+ferrous sulfate, I ₊flamprop-M, I+flazasulfuron,I+florasulam, I+fluazifop, I+fluazifop-butyl, I+fluazifop-P,I+fluazifop-P-butyl, I+fluazolate, I+flucarbazone,I+flucarbazone-sodium, I+flucetosulfuron, I+fluchloralin, I+flufenacet,I+flufenpyr, I+flufenpyr-ethyl, I+flumetralin, I+flumetsulam,I+flumiclorac, I+flumiclorac-pentyl, I+flumioxazin, I+flumipropin,I+fluometuron, I+fluoroglycofen, I+fluoroglycofen-ethyl, I+fluoxaprop,I+flupoxam, I+flupropacil, I+flupropanate, I+flupyrsulfuron,I+flupyrsulfuron-methyl-sodium, I+flurenol, I+fluridone,I+flurochloridone, I+fluroxypyr, I+flurtamone, I+fluthiacet,I+fluthiacet-methyl, I+fomesafen, I+foramsulfuron, I+fosamine,I+glufosinate, I+glufosinate-ammonium, I+glyphosate, I+halosulfuron,I+halosulfuron-methyl, I+haloxyfop, I+haloxyfop-P, I+hexazinone,I+imazamethabenz, I+imazamethabenz-methyl, I+imazamox, I+imazapic,I+imazapyr, I+imazaquin, I+imazethapyr, I+imazosulfuron, I+indanofan,I+indaziflam, I+iodomethane, I+iodosulfuron,I+iodosulfuron-methyl-sodium, I+ioxynil, I+isoproturon, I+isouron,I+isoxaben, I+isoxachlortole, I+isoxaflutole, I+isoxapyrifop,I+karbutilate, I+lactofen, I+lenacil, I+linuron, I+mecoprop,I+mecoprop-P, I+mefenacet, I+mefluidide, I+mesosulfuron,I+mesosulfuron-methyl, I+mesotrione, I+metam, I+metamifop, I+metamitron,I+metazachlor, I+methabenzthiazuron, I+methazole, I+methylarsonic acid,I+methyldymron, I+methyl isothiocyanate, I+metolachlor, I+S-metolachlor,I+metosulam, I+metoxuron, I+metribuzin, I+metsulfuron,I+metsulfuron-methyl, I+molinate, I+monolinuron, I+naproanilide,I+napropamide, I+naptalam, I+neburon, I+nicosulfuron, I+n-methylglyphosate, I+nonanoic acid, I+norflurazon, I+oleic acid (fatty acids),I+orbencarb, I+orthosulfamuron, I+oryzalin, I+oxadiargyl, I+oxadiazon,I+oxasulfuron, I+oxaziclomefone, I+oxyfluorfen, I+paraquat, I+paraquatdichloride, I+pebulate, I+pendimethalin, I+penoxsulam,I+pentachlorophenol, I+pentanochlor, I+pentoxazone, I+pethoxamid,I+phenmedipham, I+picloram, I+picolinafen, I+pinoxaden, I+piperophos,I+pretilachlor, I+primisulfuron, I+primisulfuron-methyl, I+prodiamine,I+profoxydim, I+prohexadione-calcium, I+prometon, I+prometryn,I+propachlor, I+propanil, I+propaquizafop, I+propazine, I+propham,I+propisochlor, I+propoxycarbazone, I+propoxycarbazone-sodium,I+propyzamide, I+prosulfocarb, I+prosulfuron, I+pyraclonil,I+pyraflufen, I+pyraflufen-ethyl, I+pyrasulfotole, I+pyrazolynate,I+pyrazosulfuron, I+pyrazosulfuron-ethyl, I+pyrazoxyfen, I+pyribenzoxim,I+pyributicarb, I+pyridafol, I+pyridate, I+pyriftalid, I+pyriminobac,I+pyriminobac-methyl, I+pyrimisulfan, I+pyrithiobac,I+pyrithiobac-sodium, I+pyroxasulfone, I+pyroxsulam, I+quinclorac,I+quinmerac, I+quinoclamine, I+quizalofop, I+quizalofop-P,I+rimsulfuron, I+saflufenacil, I+sethoxydim, I+siduron, I+simazine,I+simetryn, I+sodium chlorate, I+sulcotrione, I+sulfentrazone,I+sulfometuron, I+sulfometuron-methyl, I+sulfosate, I+sulfosulfuron,I+sulfuric acid, I+tebuthiuron, I+tefuryltrione, I+tembotrione,I+tepraloxydim, I+terbacil, I+terbumeton, I+terbuthylazine, I+terbutryn,I+thenylchlor, I+thiazopyr, I+thifensulfuron, I+thiencarbazone,I+thifensulfuron-methyl, I+thiobencarb, I+topramezone, I+tralkoxydim,I+tri-allate, I+triasulfuron, I+triaziflam, I+tribenuron,I+tribenuron-methyl, I+triclopyr, I+trietazine, I+trifloxysulfuron,I+trifloxysulfuron-sodium, I+trifluralin, I+triflusulfuron,I+triflusulfuron-methyl, I+trihydroxytriazine, I+trinexapac-ethyl,I+tritosulfuron,I+[3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]aceticacid ethyl ester (CAS RN 353292-31-6),I+4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoro-methyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one(CAS RN 352010-68-5), andI+4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1]oct-3-en-2-one.The compounds of the present invention may also be combined withherbicidal compounds disclosed in WO06/024820 and/or WO07/096576.

The mixing partners of the compound of Formula I may also be in the formof esters or salts, as mentioned e.g. in The Pesticide Manual,Fourteenth Edition, British Crop Protection Council, 2006.

The compound of Formula I can also be used in mixtures with otheragrochemicals such as fungicides, nematicides or insecticides, examplesof which are given in The Pesticide Manual.

The mixing ratio of the compound of Formula I to the mixing partner ispreferably from 1: 100 to 1000:1.

The mixtures can advantageously be used in the above-mentionedformulations (in which case “active ingredient” relates to therespective mixture of compound of Formula I with the mixing partner).

The compounds of Formula I according to the invention can also be usedin combination with one or more safeners. Likewise, mixtures of acompound of Formula I according to the invention with one or morefurther herbicides can also be used in combination with one or moresafeners. The safeners can be AD 67 (MON 4660), benoxacor,cloquintocet-mexyl, cyprosulfamide (CAS RN 221667-31-8), dichlormid,fenchlorazole-ethyl, fenclorim, fluxofenim, furilazole and thecorresponding R isomer, isoxadifen-ethyl, mefenpyr-diethyl, oxabetrinil,and N-isopropyl-4-(2-methoxy-benzoylsulfamoyl)-benzamide (CAS RN221668-34-4). Other possibilities include safener compounds disclosedin, for example, EP0365484. Particularly preferred are mixtures of acompound of Formula I with cyprosulfamide, isoxadifen-ethyl and/orcloquintocet-mexyl.

The safeners of the compound of Formula I may also be in the form ofesters or salts, as mentioned e.g. in The Pesticide Manual, 14^(th)Edition (BCPC), 2006. The reference to cloquintocet-mexyl also appliesto a lithium, sodium, potassium, calcium, magnesium, aluminium, iron,ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof asdisclosed in WO 02/34048, and the reference to fenchlorazole-ethyl alsoapplies to fenchlorazole, etc.

Preferably the mixing ratio of compound of Formula I to safener is from100:1 to 1:10, especially from 20:1 to 1:1.

The mixtures can advantageously be used in the above-mentionedformulations (in which case “active ingredient” relates to therespective mixture of compound of Formula I with the safener).

The present invention still further provides a method of selectivelycontrolling weeds at a locus comprising crop plants and weeds, whereinthe method comprises application to the locus of a weed controllingamount of a composition according to the present invention.‘Controlling’ means killing, reducing or retarding growth or preventingor reducing germination. Generally the plants to be controlled areunwanted plants (weeds). ‘Locus’ means the area in which the plants aregrowing or will grow.

The rates of application of compounds of Formula I may vary within widelimits and depend on the nature of the soil, the method of application(pre- or post-emergence; seed dressing; application to the seed furrow;no tillage application etc.), the crop plant, the weed(s) to becontrolled, the prevailing climatic conditions, and other factorsgoverned by the method of application, the time of application and thetarget crop. The compounds of Formula I according to the invention aregenerally applied at a rate of from 10 to 2000 g/ha, especially from 50to 1000 g/ha.

The application is generally made by spraying the composition, typicallyby tractor mounted sprayer for large areas, but other methods such asdusting (for powders), drip or drench can also be used.

Useful plants in which the composition according to the invention can beused include crops such as cereals, for example barley and wheat,cotton, oilseed rape, sunflower, maize, rice, soybeans, sugar beet,sugar cane and turf. Maize is particularly preferred.

Crop plants can also include trees, such as fruit trees, palm trees,coconut trees or other nuts. Also included are vines such as grapes,fruit bushes, fruit plants and vegetables.

Crops are to be understood as also including those crops which have beenrendered tolerant to herbicides or classes of herbicides (e.g. ALS-,GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors) by conventional methodsof breeding or by genetic engineering. An example of a crop that hasbeen rendered tolerant to imidazolinones, e.g. imazamox, by conventionalmethods of breeding is Clearfield® summer rape (canola). Examples ofcrops that have been rendered tolerant to herbicides by geneticengineering methods include e.g. glyphosate- and glufosinate-resistantmaize varieties commercially available under the trade namesRoundupReady® and LibertyLink®.

In a preferred embodiment the crop plant is rendered tolerant toHPPD-inhibitors via genetic engineering. Methods of rending crop plantstolerant to HPPD-inhibitors are known, for example from WO0246387. Thusin an even more preferred embodiment the crop plant is transgenic inrespect of a polynucleotide comprising a DNA sequence which encodes anHPPD-inhibitor resistant HPPD enzyme derived from a bacterium, moreparticularly from Pseudomonas fluorescens or Shewanella colwelliana, orfrom a plant, more particularly, derived from a monocot plant or, yetmore particularly, from a barley, maize, wheat, rice, Brachiaria,Chenchrus, Lolium, Festuca, Setaria, Eleusine, Sorghum or Avena species.

Crops are also to be understood as being those which have been renderedresistant to harmful insects by genetic engineering methods, for exampleBt maize (resistant to European corn borer), Bt cotton (resistant tocotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).Examples of Bt maize are the Bt 176 maize hybrids of NK® (SyngentaSeeds). The Bt toxin is a protein that is formed naturally by Bacillusthuringiensis soil bacteria. Examples of toxins, or transgenic plantsable to synthesise such toxins, are described in EP-A-451 878, EP-A-374753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examplesof transgenic plants comprising one or more genes that code for aninsecticidal resistance and express one or more toxins are KnockOut®(maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton),NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops or seedmaterial thereof can be both resistant to herbicides and, at the sametime, resistant to insect feeding (“stacked” transgenic events). Forexample, seed can have the ability to express an insecticidal Cry3protein while at the same time being tolerant to glyphosate.

Crops are also to be understood to include those which are obtained byconventional methods of breeding or genetic engineering and containso-called output traits (e.g. improved storage stability, highernutritional value and improved flavour).

Other useful plants include turf grass for example in golf-courses,lawns, parks and roadsides, or grown commercially for sod, andornamental plants such as flowers or bushes.

The compositions can be used to control unwanted plants (collectively,‘weeds’). The weeds to be controlled may be both monocotyledonousspecies, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus,Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria,Rottboellia, Sagittaria, Scirpus, Setaria and Sorghum, anddicotyledonous species, for example Abutilon, Amaranthus, Ambrosia,Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida,Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium. Weeds canalso include plants which may be considered crop plants but which aregrowing outside a crop area (‘escapes’), or which grow from seed leftover from a previous planting of a different crop (‘volunteers’). Suchvolunteers or escapes may be tolerant to certain other herbicides.

The compounds of the present invention can be prepared using thefollowing methods.

Preparation of compounds of the present invention is outlined in thefollowing schemes.

Preparation of compounds Formula (I)

where Q is selected from Q1 and Q5 is carried out analogously to knownprocesses (for example those described in WO97/46530, EP0353187 and U.S.Pat. No. 6,498,125) and comprises reacting a compound of the followingformula:

where the definitions R¹, R⁵, R⁶, R⁷, X¹ and X² are as for Formula (I)and LG is a suitable leaving group, for example a halogen atom, such aschlorine, or an alkoxy or aryloxy group, such as 4-nitrophenoxy, in aninert organic solvent, such as dichloromethane or acetonitrile, in thepresence of a base, such as triethylamine, with compounds

wherein

A¹ and R^(a), R^(b), R^(c), R^(d), R^(e), R^(f) and R^(i) , R^(j) are asdefined previously;

to give the following esters (3a) or (3b):

which may be rearranged using catalysts, such as4-dimethylaminopyridine, or acetone cyanhydrin, or a metal cyanide salt,such as sodium cyanide, in the presence of a suitable base, such astriethylamine, to give compounds of Formula (I). It is advantageous tohave a dehydrating agent, such as molecular sieves, present in thereaction medium to ensure any water initially present in the solvent orassociated with the other components of the reaction mixture isprevented from causing any unwanted hydrolysis of intermediates.

2-oxo or 2-thiono pyridine-3-carboxylic acid derivatives of Formulae 3aand 3b may be prepared from the corresponding 3-carboxylic acids, forexample by reaction with a suitable halogenating agent, such as oxalylchloride, in a suitable inert solvent, such as dichloromethane, togenerate the corresponding 3-carboxylic acid chlorides. Thesederivatives may in turn be reacted with, for example, 4-nitrophenol anda suitable base, such as triethylamine, in an inert solvent, such asdichloromethane, to generate the corresponding 4-nitrophenyl esters.

By way of illustration as shown in Scheme 2, 2-oxo-pyridine-3-carboxylicacid esters or 2-thionoy-pyridine-3-carboxylic acid esters of Formula 4aor Formula 4b may be obtained from 2-amino-benzaldehydes and2-amino-3-formylpyridines analogous to methods described in theliterature.

The required malonate esters are either commercially available or may beprepared analogously to methods described in the literature, for exampleCan. J. Chem. (1968), 46, 2251.

The required 2-aminobenzaldehydes and 2-amino-3-formylpyridines and areeither commercially available or may be prepared by methods described inthe literature for example Comptes Rendus des Seances de l'Academie desSciences, Serie C: Sciences Chinziques (1975), 280(6), 381-3, J. Org.Chem. (1983), 48, 3401-3408, J. Org. Chem. (1990), 55, 4744-4750 andOrg. Letts., (2002), 4, (20) 3481-3484, Synthesis (2008) 2674-2770 or byanalogous methods.

By way of illustration as shown in Scheme 3, optionally substituted2-aminopyridines may be N-acylated, for example with a suitableacylating reagent, such as acetyl chloride or pivaloyl chloride, and asuitable base, such as triethylamine, optionally with a suitableacylation catalyst such as 4-dimethylaminopyridine, in an inert solvent,such as dichloromethane, to give the correspondingN-(pyridin-2-yl)amides. Analogous to methods described in theliterature, these amides may in turn be reacted with a strong base, suchas n.butyllithium or t.butyl lithium and then a formyl transfer agent,such as N,N-dimethylformamide or N-formyl-N-methylaniline, to give thecorresponding N-(3-formylpyridin-2-yl)amides. The required2-amino-3-formylpyridines can be obtained by hydrolysis of these amidesusing, for example, aqueous hydrochloric acid heated under reflux for 1to 24 hours.

With regard to scheme 3, R′″ is for example, C₁-C₆ alkyl.

Alternatively, as shown in Scheme 4, 2-aminopyridine-3-carboxylic estersmay be reduced, using a suitable reducing agent, such as lithiumaluminium hydride, in a suitable solvent, such as tetrahydrofuran, to2-amino-3-hydroxymethylpyridines and subsequently oxidised, using asuitable oxidising agent, such as manganese dioxide, in a suitablesolvent , such as dichloromethane, to the required2-amino-3-formylpyridines.

Alternatively, as shown in Scheme 4a, a pyridine aldehyde substituted onthe amino group (R¹ not=H) may be prepared from a pyridine aldehyde(R¹═H) by N-substitution with an aryl or heteroaryl bromide in thepresence of a suitable palladium catalyst and ligand, for examplePd2(dba)3 and Xantphos, in a suitable solvent such as dioxane, in thepresence of a base, such as caesium carbonate.

Alternatively as shown in Scheme 4b, a pyridine aldehyde substituted onthe amino group (R¹ not ═H) may be prepared from a 2-chloro-pyridinealdehyde by reaction with an amine, for example in the presence of asuitable palladium catalyst and ligand, for example Pd2(dba)3 andXantphos, in a suitable solvent such as dioxane, in the presence of abase, such as caesium carbonate.

As shown in Scheme 5, 2-oxopyridine ester derivatives where R¹ ishydrogen, may be further reacted with alkylating agents or arylating orheteroarylating agents using procedures described in the literature (forexample Tetrahedron, (1999), 55, 12757-12770 or by analogousprocedures).

As shown in Scheme 6, pyridyl-3-carboxylic acid esters derivatives ofFormula 6 may be conveniently hydrolysed to the corresponding carboxylicacids (7) using standard procedures, for example using aqueous sodiumhydroxide and a co-solvent such as ethanol, or lithium hydroxide inaqueous tetrahydrofuran.

As shown in Scheme 7, 2-oxopyridyl-3-carboxylic acid esters of Formula 8may be conveniently converted to the corresponding N-oxides using asuitable oxidant, such as a peracid, for example per-trifluoroaceticacid generated from urea hydrogen peroxide complex and trifluoroaceticacid anhydride.

The N-oxides generated may be farther reacted with a suitable acidhalide reagent, such as phosphoryl chloride, optionally with a suitablebase, such as triethylamine, in a suitable solvent, such asdichloromethane or 1,2-dichloroethane, at 20° C. to 100° C. to give the7-halo derivatives.

With regard to Scheme 7, R^(i) is, for example, C₁-C₄ alkyl.

As shown in Scheme 8, 7-halo-2-oxo or7-halo-2-thiono-[1,8]-naphthyridines may be further transformed intoadditional 7-substituted-2-oxo or 2-thiono-[1,8]-naphthyridines usefulfor preparing compounds of Formula (I). For example, when R⁵ is hydrogenor methyl and R⁷ is a chlorine atom, the chlorine may be displaced by analkoxide reagent, such as sodium ethoxide, in a suitable solvent, suchas tetrahydrofuran or N,N-dimethylformamide or an alcohol, such asethanol, to generate the corresponding 7-alkoxy-2-oxo or7-alkoxy-2-thiono-[1,8]-naphthyridine derivative. Similarly,7-halo-2-oxo- or 7-halo-2-thiono-[1,8]-naphthyridines may be reactedwith an amine, such as morpholine, in a suitable solvent, such astetrahydrofuran, to generate the corresponding 7-alkylamino-2-oxo- or7-alkylamino-2-thiono-[1,8]-naphthyridines or 7-dialkylamino-2-oxo- or7- dialkylamino-2-thiono-[1,8]-naphthyridines. Additionally,7-halo-2-oxo or 7-halo-2-thiono-[1,8]-naphthyridines, such as7-chloro-2-oxo or 7-chloro-2-thiono-[1,8]-naphthyridines, 7-alkoxy-2-oxoor 7-alkoxy-2-thiono-[1,8]-naphthyridines, such as 7-methoxy-2-oxo or7-methoxy-2-thiono-[1,8]-naphthyridines, may be converted to7-hydroxy-2-oxo or 7-hydroxy-2-thiono-[1,8]-naphthyridines, for exampleby hydrolysis under acidic conditions, such as heating with aqueoushydrochloric acid. Such reactions may be conducted at temperatures from20° C. to 150° C., for example in a microwave oven. Additionally,7-hydroxy-2-oxo or 7-hydroxy-2-thiono-[1,8]-naphthyridines may betransformed to the corresponding 7-haloalkanesulfonate esters of[1,8]naphthyridines, such as 2-oxo or 2-thiono-7-trifluoromethanesulfonyloxy[1,8]naphthyridines, with a suitableacylation agent, such as trifluoromethane sulfonic anhydride, and asuitable base, such as triethylamine, in a suitable solvent , such asdichloromethane. In another aspect, 7-halo-2-oxo or7-halo-2-thiono-[1,8]-naphthyridines, such as 7-chloro-2-oxo or7-chloro-2-thiono-[1,8]-naphthyridines, or 7-haloalkanesulfonate estersof [1,8]naphthyridines, such as 2-oxo or 2-thiono-7-trifluoromethanesulfonyloxy[1,8]naphthyridines, may be reacted with analkyl or aryl or heteroaryl boronic acid reagent, such as methyl boronicacid or phenyl boronic acid or 3-thienylboronic acid, in the presence ofa palladium catalyst, such as palladium acetate, and a suitable basesuch as potassium phosphate and a suitable palladium ligand, such asdicyclohexyl-(2′,6′-dimethoxybiphenyl-2-yl) phosphane, to generate7-methyl or 7-phenyl or 7-(thienyl-3-yl) 2-oxo- or2-thiono[1,7]naphthyridine derivatives.

EXAMPLES

Abbreviations as used in the following Examples are as follows:s=singlet, d=doublet, t=triplet, m=multiplet, bs=broad signal, bm=broadmultiplet, dd=double doublet, dt=double triplet, td=triple doublet anddq=double quartet.

Example 1 Preparation of2-(6-fluoro-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carbonyl)-cyclohexane-1,3-dioneStage 1 Preparation ofN-(5-fluoro-pyridin-2-yl)-2,2-dimethylpropionamide

To a stirred solution of 2-amino-5-fluoropyridine (50.0 g, commerciallyavailable) and triethylamine (93 ml) in dichloromethane (600 ml) wasadded pivaloyl chloride (56 ml) at ambient temperature. The slurry thatformed was stirred for 3 hours, stored for 18 hours then washed withwater (200 ml), brine (100 ml) then dried over magnesium sulfate,filtered and evaporated under reduced pressure to give the requiredproduct as a brown oil, 86 g. ¹HNMR (CDCl₃) δ: 8.30(1H, dd), 8.10(1H,d), 8.00(1H, bs), 7.42(1H, m), 1.30(9H, s).

In a similar procedure,N-(6-methylpyridin-2-yl)-2,2-dimethylpropionamide was prepared from2-amino-6-methylpyridine. ¹HNMR (CDCl₃) δ: 8.02-8.04(1H, d), 7.95(1H,broad s), 7.54-7.60(1H, t), 6.86-6.88(1H, d), 2.44(311, s), 1.31(9H, s).Similarly, N-(5-fluoro-6-methylpyridin-2-yl)-2,2-dimethylpropionamidewas prepared from 2-amino-5-fluoro-6-methylpyridine. ¹H NMR (CDCl₃) δ:8.02 (1H, dd), 7.95(1H, broad s), 7.35(1H, t), 2.44(3H, d), 1.32(9H, s).

Stage 2 Preparation ofN-(5-fluoro-3-formyl-pyridin-2-yl)-2,2-dimethylpropionamide

To a stirred solution ofN-(5-fluoro-pyridin-2-yl)-2,2-dimethylpropionamide (39.2 g) in drydiethyl ether (1200 ml) under an atmosphere of nitrogen at −78° C. wasadded dropwise t.-butyl lithium in hexanes (1.7M, 300 ml). The mixturewas stirred at −78° C. for 2 hours then dry N,N-dimethylformamide (160ml) was added and the slurry stirred at −78° C. for 1 hour then allowedto slowly warm to ambient temperature and stirred for an additional 1hour. The mixture was quenched with aqueous 2M hydrochloric acid until aclear biphasic solution was formed and the organic phase separated. Theaqueous phase was further extracted with diethyl ether. The extractswere combined, washed with brine (300 ml), dried over magnesium sulfate,filtered and evaporated under reduced pressure to give the requiredproduct as a pale yellow solid, 40 g. ¹H NMR (CDCl₃) δ: 11.20(1H, s),9.94(1H, s), 8.59(1H, d), 7.84(1H, dd), 1.42(9H, s).

In a similar procedure,N-(3-formyl-6-methylpyridin-2-yl)-2,2-dimethylpropionamide was preparedfrom N-(6-methylpyridin-2-yl)-2,2-dimethylpropionamide ¹H NMR (CDCl₃) δ:10.9 (1H, broad s), 9.88(1H, s), 7.89-7.91(1H, d), 7.03-7.05(1H, d),2.64(3H, s), 1.38(9H, s).

Similarly,N-(5-fluoro-3-formyl-6-methylpyridin-2-yl)-2,2-dimethylpropionamide wasprepared from N-(5-fluoro-6-methylpyridin-2-yl)-2,2-dimethylpropionamide¹H NMR (CDCl₃) δ: 10.15 (1H,s), 9.82 (1H, s), 7.68 (1H, d), 2.60(3H, d),1.38(9H, s),

Similarly,N-(3-formyl-6-methoxymethylpyridin-2-yl)-2,2-dimethylpropionamide wasprepared from N-(6-methoxymethylpyridin-2-yl)-2,2-dimethylpropionamide,brown oil, ¹HNMR (CDCl₃) δ: 9.91(1H, s), 8.04(1H, d), 7.36(1H, d),4.66(2H, s), 3.51(3H, s), 1.37(9H, s).

Stage 3 Preparation of 2-amino-5-fluoropyridinyl-3-carboxaldehyde

A mixture of N-(5-fluoro-3-formyl-pyridin-2-yl)-2,2-dimethylpropionamide(14.2 g) in aqueous 2M hydrochloric acid (200 ml) was stirred at 100° C.for 45 minutes, cooled to ambient temperature, treated with sodiumhydrogen carbonate until the mixture was pH 5 then extracted withdichloromethane (2×100 ml). The extracts were combined, washed withaqueous sodium hydrogen carbonate (50 ml) then water (50 ml), dried overmagnesium sulfate, filtered and evaporated under reduced pressure togive the required product as a yellow solid, 6.5 g. ¹HNMR (CDCl₃) δ:9.82(1H, s), 8.18(1H, d), 7.54(1H, dd), 6.62(2H, bs).

In a similar procedure, 2-amino-6-methylpyridinyl-3-carboxaldehyde wasprepared fromN-(3-formyl-6-methylpyridin-2-yl)-2,2-dimethylpropionamide, ¹H NMR(CDCl₃) δ: 9.80(1H, s), 7.68-7.70(1H,d), 6.56-6.58(1H,d), 2.42(3H,s).

Similarly, 2-amino-5-fluoro-6-methylpyridinyl-3-carboxaldehyde wasprepared fromN-(5-fluoro-3-formyl-6-methylpyridin-2-yl)-2,2-dimethylpropionamide, ¹HNMR (CDCl₃) δ: 9.78 (1H, s), 7.43(1H,d), 2.42(3H,d).

Other carboxaldehydes useful in the present invention can be prepared,for example, in the following manner.

Preparation of5-fluoro-2-(2-trifluoromethyl-phenylamino)-pyridine-3-carboxyaldehyde

A mixture of 2-amino-5-fluoro-pyridine-3-carbaldehyde (680 mg),2-bromo-trifluoromethylbenzene (1.02 ml), Pd(dba-3,5,3′,5′-OMe)₂(407mg), Xantphos (290 mg) and caesium carbonate (2.28 g) in dioxane (10 ml)was heated at 150° C. in the microwave for 30 minutes. The reactionmixture was allowed to cool to room temperature, filtered, thenevaporated under reduced pressure. The residue was purified by columnchromatography (silica; ethyl acetate/hexane) to give the requiredproduct as a yellow solid (1.05 g).

Preparation of2-(5-trifluoromethyl-isoxazol-3-ylamino)-pyridine-3-carboxyaldehyde

A mixture of 2-bromo-pyridine-3-carbaldehyde (280 mg),5-trifluoromethyl-isoxazol-3-ylamine (152 mg), Pd(dba-3,5,3′,5′-OMe)₂(85 mg), Xantphos (58 mg) and caesium carbonate (455 mg) in toluene (3ml) was heated at 150° C. in the microwave for 35 minutes. The reactionmixture was allowed to cool to room temperature, filtered, thenevaporated under reduced pressure. The residue was purified by columnchromatography (silica; ethyl acetate/hexane) to give the requiredproduct as a yellow solid (120 mg).

Stage 4 Preparation of ethyl6-fluoro-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carboxylate

A mixture of 2-amino-5-fluoropyridine-3-carboxaldehyde (2.80 g), diethylmalonate (6.40 g) and piperidine (0.85 g) in ethanol (50 ml) were heatedto reflux with stirring for 18 hours, allowed to cool to ambienttemperature then evaporated under reduced pressure. The residual solidobtained was washed with diethyl ether then filtered from solution, andsucked to dryness to give the required product as a pale brown solid,3.97 g. ¹H NMR (CDCl₃) δ: ca 11.0(1H, bs), 9.33(1H, m), 8.66(1H, d),8.42(1H, s), 7.74(1H, m), 4.45(2H, q), 1.44(3H, t).

The following compounds were prepared using a similar procedure:

From 2-amino-6-methylpyridine-3-carboxaldehyde, ethyl7-methyl-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carboxylate, orangesolid, m.p.153-156° C., ¹H NMR (CDCl₃) δ: 8.46(1H, s), 7.87(1H, d),7.10(1H, d), 4.43(2H, q), 2.68(3H, s), 1.42(3H, t). From2-amino-5-fluoro-6-methylpyridine-3-carboxaldehyde, ethyl6-fluoro-7-methyl-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carboxylate,orange-brown solid, ¹H NMR (CDCl₃) δ: 8.40(1H, s), 7.59(1H, d), 4.43(2H,q), 2.62(3H, d), 1.42(3H, t).

Stage 5 Preparation of ethyl6-fluoro-1-methyl-2-oxo-1,2-dihydro[1,8]-naphthwidine-3-carboxylate

To a stirred suspension of sodium hydride (0.11 g, 60% dispersion inmineral oil) in dry N,N-dimethylfonnamide (2 ml) at ambient temperatureunder an atmosphere of nitrogen was added a solution of ethyl6-fluoro-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carboxylate (0.61 g) indry N,N-dimethylformamide (20 ml) over 10 minutes. The mixture wasstirred for 30 minutes then a solution of methyl iodide (0.55 g) in dryN,N-dimethylformamide (2 ml) was added over 5 minutes. The mixture wasstirred for 2 hours then stored for 18 hours at ambient temperature. Thedark orange solution was poured into water and extracted with ethylacetate (three times). The extracts were combined, washed with water(three times), dried over magnesium sulfate, filtered and evaporatedunder reduced pressure. The residual solid was washed with isohexanethen filtered from solution and sucked to dryness to give the requiredproduct as a paler yellow solid, 0.47 g. ¹HNMR (CDCl₃) δ: 8.58(1H, d),8.28(1H, s), 7.70(1H, d), 4.45(2H, q), 3.86(3H, s), 1.42(3H, t).

The following compounds were prepared using a similar procedure:

From ethyl 7-methyl-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carboxylate,ethyl 1,7-methyl-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carboxylate,yellow solid, ¹H NMR (CDCl₃) δ: 8.34(1H, s), 7.83(1H, d), 7.10(1H, d),4.43(2H, q), 3.86?(3H, s), 2.68(3H, s), 1.42(3H, t).

From ethyl6-fluoro-7-methyl-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carboxylate,ethyl6-fluoro-1,7-dimethyl-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carboxylate,orange solid, ¹HNMR (CDC/₃) δ: 8.26(1H, s), 7.57(1H, d), 4.43(2H, q),3.84(3H,s), 2.64(3H, d), 1.42(3H, t).

Stage 6 Preparation of6-fluoro-1-methyl-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carboxylic acid

To a stirred suspension of ethyl6-fluoro-1-methyl-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carboxylate(0.46 g) in ethanol (15 ml) was added a solution of lithium hydroxidemonohydrate (0.10 g) in water (5 ml) at ambient temperature. The mixturewas stirred for 2 hours, evaporated under reduced pressure to a smallvolume, diluted with water then acidified with aqueous 2M hydrochloricacid. The solid formed was filtered from solution and sucked to drynessto give the required product as a colourless solid, 0.39 g. ¹HNMR(CDCl₃+d6-DMSO) δ: 14.4(1H, s), 8.92(1H, s), 8.72(1H, d), 7.94(1H, m),3.98(3H, s).

The following compounds were prepared using a similar procedure from thecorresponding carboxylic esters:

1,7-Methyl-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carboxylic acid,yellow solid, ¹H NMR (CDCl₃+d6-DMSO) δ: 14.5(1H, s), 8.88(1H, s),8.05(1H, d), 7.27(1H, d), 3.98(3H, s), 2.74(3H, s).

6-Fluoro-1,7-dimethyl-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carboxylicacid, orange solid, ¹H NMR (CDCl₃) δ: 14.4(1H, s), 8.84(1H, s), 7.75(1H,d), 3.98(3H,s), 2.72(3H, d).

Stage 7

To a stirred suspension of6-fluoro-1-methyl-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carboxylic acid(0.38 g) in dry dichloromethane (20 ml) containing dryN,N-dimethylformamide (0.05 ml) was added oxalyl chloride (0.26 g). Themixture was stirred for 1.5 hours then evaporated under reducedpressure. The residue was suspended in dry acetonitrile (15 ml) withstirring and powdered 3 A molecular sieves were added followed by1,3-cyclohexanedione (0.22 g) and dry triethylamine (0.24 ml). Themixture was stirred at ambient temperature for 2 hours then further drytriethylamine (0.47 ml) added followed by acetone cyanhydin (0.05 ml).The mixture was stirred for 18 hours, acidified with aqueoushydrochloric acid then extracted with ethyl acetate (three times). Theextracts were combined, washed with water, dried over magnesium sulfate,filtered and evaporated under reduced pressure to a gum. The gum waspurified by chromatography (silica;toluene/dioxane/triethylamine/ethanol/water, 100:40:20:20:5 by volume)to give, on acidification of the isolated triethylamino salt, therequired product as a yellow, foamy solid (0.18 g). ¹HNMR (CDCl₃) δ:16.4(1H, s), 8.50(1H, d), 7.63(1H, s), 7.62(1H, m), 3.80(3H, s),2.78(2H, t), 2.49(2H, t), 2.08(2H, m).

The following compounds were prepared using a similar procedure from thecorresponding carboxylic acids:

2-(6-Fluoro-7-methyl-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carbonyl)-cyclohexane-1,3-dione,yellow solid, m.p.191-193° C., ¹HNMR (CDCl₃) δ: 16.4(1H, s), 7.62(1H,s), 7.51(1H, d), 3.80(3H, s), 2.76(2H, t), 2.63(3H, s), 2.49(2H, t),2.07(2H, m).

2-(1,7-Dimethyl-2-oxo-1,2-dihydro[1,8]-naphthyridine-3-carbonyl)-cyclohexane-1,3-dione,yellow solid, ¹HNMR (CDCl₃) δ: 16.5(1H, s), 7.78(1H, d), 7.70(1H, s),7.04(1H, d), 3.80(3H, s), 2.75(2H, t), 2.65(3H, s), 2.49(2H, t),2.07(2H, m).

Thus, according to the present invention there is further provided amethod of making a compound of Formula (I) wherein Q=Q1 which comprisesreacting together a compound of Formula (Ia′)

wherein the various substituents are as defined previously, and whereinR¹² is halogen or aryloxy with a compound of Formula (II)

wherein the various substituents are as defined previously, in thepresence of an inert organic solvent and a base. The method may furthercomprise a subsequent rearrangement step known to the skilled personusing, for example, a suitable catalyst, for example acetone cyanhydrin.

Preferably R¹² is selected from the group consisting of fluorine,chlorine, bromine, and 4-nitrophenoxy. In an especially preferredembodiment R¹² is chlorine.

The present invention still further provides a compound of Formula (III)

wherein

-   R¹, R⁵, R⁶, R⁷, X¹, X² are as defined herein; and-   R¹³ is selected from the group consisting of halogen, C₁-C₆-alkoxy,    OH, O⁻M⁺ wherein M⁺ is an alkali metal cation or an ammonium cation    with the exception of    1,6,7-Trimethyl-2-oxo-1,2-dihydro-quinoline-3-carboxylic acid,    1,6,7-Trimethyl-2-oxo-1,2-dihydro-quinoline-3-carboxylic acid methyl    ester,    1,2-dihydro-2-oxo-1-[3-(trifluoromethyl)phenyl-1,8-naphthyridine-3-carboxylic    acid and    1,2-dihydro-2-oxo-1-[3-(trifluoromethyl)phenyl-1,8-naphthyridine-3-carboxylic    acid ethyl ester.

The present invention further provides the use of a compound of Formula(I) as a herbicide.

Examples of specific compounds of the present invention.

TABLE 1

Cmp R¹ R⁵ R⁶ R⁷ NMR 1.1 CH₃ H H H 1.2 CH₃ H H CH₃ 1.3 CH₃ H H Et, 1.4CH₃ H H n-Propyl 1.5 CH₃ H H i-Propyl 1.6 CH₃ H H c-Propyl 1.7 CH₃ H Hn-Butyl 1.8 CH₃ H H i-Butyl 1.9 CH₃ H H s-Butyl 1.10 CH₃ H H c-Butyl1.11 CH₃ H H CH₂F 1.12 CH₃ H H CF₂H 1.13 CH₃ H H CF₃ 1.14 CH₃ H H C₂F₅1.15 CH₃ H H CH₂OCH₃ 1.16 CH₃ H H O-cPentyl 1.17 CH₃ H H O—Ph 1.18 CH₃ HH OCH(CH₃) CH₂CH₂CH₂CH₃ 1.19 CH₃ H F CH₃ 1.20 CH₃ H H SO₂Me 1.21 CH₃ H HOH 1.22 CH₃ H H OCH(CH₃)₂ 1.23 CH₃ H H OCH₃ 1.24 CH₃ H H CF₃ 1.25 CH₃ HCH₃ H 1.26 CH₃ H H OC₂H₅ 1.27 CH₃ H H Cl 1.28 CH₃ H F H 1.29 CH₃ H H H2.04-2.10(2H, m); 2.48-2.52(2H, t); 2.74- 2.80(2H, t); 3.82(3H, s);7.18-7.22(1H, m); 7.70(1H, s); 7.90-7.92(1H, dd); 8.63- 8.65(1H, dd);16.5(1H, s). 1.30 CH₃ H H OC₂H₅ 1.31 CH₃ H H OC₂H₅ 1.32 CH₃ H Cl H 1.33CH₃ H H H 1.34 CH₃ H H H 1.35 CH₃ H H CHFCH₃ 1.36 CH₃ H H CF₂CH₃ 1.37CH₃ H H CF(CH₃)₂ 1.38 CH₃ H F CHFCH₃ 1.39 CH₃ H F CF₂CH₃ 1.40 CH₃ H FCF(CH₃)₂ 1.41 CH₃ H F CH₃ 1.42 CH₃ CH₃ H CH₃ 2.05-2.11(2H, m);2.48-2.52(2H, t); 2.53(3H, s); 2.59(3H, s); 2.72-2.76(2H, t); 3.80(3H,s); 6.99(1H, s); 7.94(1H, s); 16.5(1H, s). 1.43 methoxymethyl H F H2.05-2.11(2H, m); 2.46-2.50(2H, t); 2.76- 2.80(2H, t); 3.50(3H, s);5.92(2H, s); 7.60- 7.64(1H, m); 7.63(1H, s); 8.53-8.55(1H, d); 16.4(1H,s). 1.44 methoxyethyl H F H 2.04-2.12(2H, m); 2.46-2.50(2H, br t); 2.74-2.78(2H, br t); 3.36(3H, s); 3.68-3.72(2H, t); 4.72-4.76(2H, t);7.60-7.64(1H, m); 7.64(1H, s); 8.50(1H, d); 16.4(1H, s). 1.45 2,2 H F H2.04-2.12(2H, m); 2.42-2.52(2H, br s); 2.70- difluoroethyl 2.80(2H, brs); 4.90-4.98(2H, dt); 6.02-6.34(1H, tt); 7.64-7.68(2H, s & dd));8.49-8.50(1H, d); 16.3(1H, s). 1.46 methoxymethyl H F CH₃ 2.04-2.10(2H,m); 2.44-2.50(2H, br t); 2.63(3H, d); 2.72-2.78(2H, br t); 3.50(3H, s);5.94(2H, s); 7.50-7.52(1H, d); 7.63(1H, s); 16.4(1H, s). 1.47methoxyethyl H F CH₃ 1.98-2.04(2H, m); 2.38-2.42(2H, t); 2.54(3H, d);2.66-2.70(2H, t); 3.32(3H, s); 3.61-3.65(2H, t); 4.65-4.69(2H, t);7.43-7.45(1H, d); 7.55(1H, s); 16.3(1H, s). 1.48 1,1-difluoro- H F H2.04-2.12(2H, m); 2.40-2.50(4H, m); 2.74- but-1-enyl 2.78(2H, t);4.22-4.32(1H, 2 x t); 4.50- 4.54(2H, t); 7.62-7.64(2H, m); 8.50(1H, d);16.3(1H, s). 1.49 ethyl H F H 1.28-1.34(3H, t); 2.06-2.12(2H, m); 2.46-2.50(2H, t); 2.74-2.78(2H, t); 4.52-4.56(2H, q); 7.60-7.62(2H, m);8.50-8.51(1H, d); 16.4(1H, s). 1.50 propyl H F H 0.98-1.02(3H, t);1.70-1.78(2H, m); 2.06- 2.12(2H, m); 2.46-2.52(2H, br s); 2.72- 2.78(2H,br s); 4.40-4.46(2H, t); 7.60- 7.64(2H, m); 8.49-8.50(1H, d); 16.4(1H,s). 1.51 i-Butyl H F H 0.92-0.94(6H, d); 2.06-2.12(2H, m); 2.26-2.34(1H, m); 2.46-2.50(2H, t); 2.74-2.78(2H, t); 4.44-4.46(1H, d);7.58-7.62(2H, m); 8.48- 8.49(1H, d); no enol H 1.52 1-propenyl H F H2.04-2.10(2H, m); 2.42-2.54(2H, br s); 2.70- 2.80(2H, br s);5.00-5.22(4H, m); 5.92- 6.02(1H, m); 7.62-7.66(2H, m); 8.49-8.50(1H, d);16.4(1H, s).

TABLE 2

Compound R¹ R⁵ R⁶ R⁷ 2.1 CH₃ H H H 2.2 CH₃ H H CH₃ 2.3 CH₃ H H Et, 2.4CH₃ H H n-Propyl 2.5 CH₃ H H i-Propyl 2.6 CH₃ H H c-Propyl 2.7 CH₃ H Hn-Butyl 2.8 CH₃ H H i-Butyl 2.9 CH₃ H H s-Butyl 2.10 CH₃ H H c-Butyl2.11 CH₃ H H CH₂F 2.12 CH₃ H H CF₂H 2.13 CH₃ H H CF₃ 2.14 CH₃ H H C₂F₅2.15 CH₃ H H CH₂OCH₃ 2.16 CH₃ H H O-cPentyl 2.17 CH₃ H H O—Ph 2.18 CH₃ HH OCH(CH₃)CH₂CH₂CH₂CH₃ 2.19 CH₃ H F CH₃ 2.20 CH₃ H H SO₂Me 2.21 CH₃ H HOH 2.22 CH₃ H H OCH(CH₃)₂ 2.23 CH₃ H H OCH₃ 2.24 CH₃ H H CF₃ 2.25 CH₃ HCH₃ H 2.26 CH₃ H H OC₂H₅ 2.27 CH₃ H H Cl 2.28 CH₃ H F H 2.29 CH₃ H H H2.30 CH₃ H H OC₂H₅ 2.31 CH₃ H H OC₂H₅ 2.32 CH₃ H Cl H 2.33 CH₃ H H H2.34 CH₃ H H H 2.35 CH₃ H H CHFCH₃ 2.36 CH₃ H H CF₂CH₃ 2.37 CH₃ H HCF(CH₃)₂ 2.38 CH₃ H F CHFCH₃ 2.39 CH₃ H F CF₂CH₃ 2.40 CH₃ H F CF(CH₃)₂2.41 CH₃ H F CH₃

TABLE 3

Cmp R¹ R⁵ R⁶ R⁷ R⁸ NMR 3.1 CH₃ H H H CH₃ 3.2 CH₃ H H CH₃ CH₃ 3.3 CH₃ H HEt, CH₃ 3.4 CH₃ H H n-Propyl CH₃ 3.5 CH₃ H H i-Propyl CH₃ 3.6 CH₃ H Hc-Propyl CH₃ 3.7 CH₃ H H n-Butyl CH₃ 3.8 CH₃ H H i-Butyl CH₃ 3.9 CH₃ H Hs-Butyl CH₃ 3.10 CH₃ H H c-Butyl CH₃ 3.11 CH₃ H H CH₂F CH₃ 3.12 CH₃ H HCF₂H CH₃ 3.13 CH₃ H H CF₃ CH₃ 3.14 CH₃ H H C₂F₅ CH₃ 3.15 CH₃ H H CH₂OCH₃CH₃ 3.16 CH₃ H H O-cPentyl CH₃ 3.17 CH₃ H H O—Ph CH₃ 3.18 CH₃ H HOCH(CH₃)CH₂CH₂CH₂CH₃ CH₃ 3.19 CH₃ H F CH₃ CH₃ 3.20 CH₃ H H SO₂Me CH₃3.21 CH₃ H H OH CH₃ 3.22 CH₃ H H OCH(CH₃)₂ CH₃ 3.23 CH₃ H H OCH₃ CH₃3.24 CH₃ H H CF₃ CH₃ 3.25 CH₃ H CH₃ H CH₃ 3.26 CH₃ H H OC₂H₅ CH₃ 3.27CH₃ H H Cl CH₃ 3.28 CH₃ H F H CH₃ 3.29 CH₃ H H H CH₃ 3.30 CH₃ H H OC₂H₅CH₃ 3.31 CH₃ H H OC₂H₅ CH₃ 3.32 CH₃ H Cl H CH₃ 3.33 CH₃ H H H CH₃ 3.34CH₃ H H H CH₃ 3.35 CH₃ H H CHFCH₃ CH₃ 3.36 CH₃ H H CF₂CH₃ CH₃ 3.37 CH₃ HH CF(CH₃)₂ CH₃ 3.38 CH₃ H F CHFCH₃ CH₃ 3.39 CH₃ H F CF₂CH₃ CH₃ 3.40 CH₃H F CF(CH₃)₂ CH₃ 3.41 CH₃ H F CH₃ CH₃ 3.42 CH₃ H H Br H 2.04-2.10(2H,m); 2.46-2.50(2H, t); 2.72-2.76(2H, t); 3.67(3H, s); 7.34- 7.38(1H, dd);7.44-7.48(1H, d); 7.52(1H, s); 7.69(1H, s); 16.5(1H, s).

TABLE 4

Cmp R¹ R⁵ R⁶ R⁷ NMR 4.1

H H H 4.2

H H  H, (1H, dd), 7.96 (1H, dd), 7.82 (1H, s), 7.56 (2H, t), 7.48 (1H,t), 7.32 (2H, d), 7.18 1H, dd). 2.70 (2H, bs), 2.46 (bs), 2.20 (2H,quintet) 4.3

H F H 2.00-2.06(2H, m); 2.42-2.48(2H, br t); 2.70- 2.74(2H, t);7.05-7.07(1H, dd); 7.36-7.37(1H, d); 7.46-7.50(1H, m); 7.64-7.68(1H,dd); 7.70(1H, s); 8.39-8.40(1H, d); 16.3(1H, s). 4.4

H F H 2.00-2.06(2H, m); 2.40-2.58(2H, br s); 2.58- 2.78(2H, br t);7.29-7.31(2H, d); 7.46- 7.50(1H, m); 7.54-7.58(2H, m); 7.66- 7.70(1H,dd); 7.74(1H, s); 8.34(1H, d); 16.3(1H, s). 4.5

H F CF₃ 4.6

H F CF₃ 4.7

H H CH₃ 4.8

H H CH₃ 4.9

H F CH₃ 2.00-2.06(2H, m); 2.44-2.46(3H, d); 2.50- 2.64(4H, br s);7.04-7.06(1H, d); 7.34(1H, d); 7.40-7.44(1H, m); 7.53-7.55(1H, d);7.70(1H, s); 16.3(1H, hump). 4.10

H F CH₃ 2.00-2.06(2H, m); 2.40-2.42(3H, d); 2.44- 2.48(2H, br t);2.70-2.74(2H, br t); 7.26- 7.28(2H, d); 7.43-7.47(1H, m); 7.50- 7.58(3H,m); 7.74(1H, s); 16.4(1H, s). 4.11 3-CF₃- H F H 2.00-2.08(2H, m);2.40-2.50(2H, br s); 2.70- phenyl- 2.78(2H, br s); 7.50-7.54(1H, m);7.58(1H, s); 7.64-7.74(4H, m); 8.30(1H, d); 16.3(1H, s). 4.12

H F H 2.00-2.06(2H, m); 2.40-2.55(2H, br s); 2.55- 2.75(2H, br s);4.30(4H, s); 6.74-6.78(1H, dd); 6.84(1H, s); 7.00-7.02(1H, d);7.64-7.68(tH, dd); 7.72(1H, s); 8.39(1H, d); 16.3(1H, s). 4.13

H F H 2.00-2.08(2H, m); 2.40-2.50(2H, br s); 2.68- 2.76(2H, br s);6.04-6.08(2H, d); 6.74- 6.78(1H, d); 6.76(1H, s); 6.94-6.96(1H, d);7.65- 7.69(1H, dd); 7.72(1H, s); 8.39(1H, d); 16.3(1H, s). 4.14 -benzylH F H 2.04-2.10(2H, m); 2.46-2.54(2H, br s); 2.72- 2.80(2H, br s);5.69(2H, s); 7.18-7.28(3H, m); 7.42-7.46(2H, d); 7.60-7.64(2H, m); 8.47-8.48(1H, d); 16.4(1H, s). 4.15 2- H F H 2.02-2.10(2H, m); 2.44-2.48(2H,t); 2.72- fluorobenzyl 2.76(2H, t); 5.76(2H, s); 6.96-7.08(3H, m); 7.14-7.20(1H, m); 7.62-7.66(1H, dd); 7.68(1H, s); 8.42-8.43(1H, d); 16.3(1H,s). 4.16 Phenoxyethyl- H F H 2.04-2.12(2H, m); 2.46-2.50(2H, t); 2.74-2.78(2H, t); 4.26-4.30(2H, t); 4.90-4.94(2H, t); 6.90-6.92(3H, m);7.23-7.25(2H, d); 7.61- 7.65(2H, m); 8.49-8.50(1H, d); 16.4(1H, s). 4.174- H F H 2.04-2.12(2H, m); 2.48-2.52(2H, br t); 2.74- methoxybenzyl2.78(2H, t); 3.74(3H, s); 5.62(2H, s); 6.78- 6.80(2H, d); 7.42-7.44(2H,d); 7.58-7.62(2H, m); 8.59-8.60(1H, d); 16.4(1H, s). 4.18 4- H F H2.00-2.06(2H, m); 2.42-2.48(2H, br t); 2.70- methoxyphenyl 2.74(2H, t);3.86(3H, s); 7.04-7.06(2H, m); 7.20- 7.22(2H, m); 7.65-7.69(1H, dd);7.73(1H, s); 8.37-8.38(1H, d); 16.3(1H, s). 4.19 3- H F H 1.38-1.42(3H,t); 2.00-2.08(2H, m); 2.42- ethoxyphenyl 2.46(2H, br t); 2.70-2.74(2H,t); 4.00-4.08(2H, br q); 6.80-7.24 (3H, m); 7.42-7.46(1H, t); 7.66-7.70(1H, dd); 7.74(1H, s); 8.36-8.37(1H, m); 16.3(1H, s). 4.202-methoxy- H F H 2.00-2.06(2H, m); 2.42-2.46(2H, br t); 2.71-pyridin-5-yl 2.75(2H, t); 4.00(3H, s); 6.90-6.92(1H, d); 7.50- 7.54(1H,dd); 7.66-7.70(1H, dd); 7.74(1H, s); 8.12-8.13(1H, d); 8.34-8.35(1H, d);16.3(1H, s). 4.21 phenyl H H methoxy 16.41 (1H, brs), 7.89 (1H, s), 7.82(1H, d), 7.53- 7.49 (2H, m), 7.44-7.40(1H, m), 7.31-7.28 (2H, m), 6.62(1H, d), 3.55 (3H, s), 2.69 (2H, t), 2.47 (2H, t), 2.02 (2H, qn). 4.222- H F H 16.22 (1H, s), 8.36 (1H, d), 7.78 (1H, 1), 7.68 methylphenyl(1H, dd), 7.33-7.42 (3H, m), 7.14 (1H, d), 2.71 (2H, t), 2.40-2.48 (2H,m), 2.09 (3H, s), 2.00- 2.06 (2H, m) 4.23 3,5- H F H 2.00-2.08(2H, m);2.44-2.48(2H, br t); 2.72- dichlorophenyl 2.76(2H, t); 7.24(2H, s);7.47-7.48(1H, t); 7.66- 7.70(1H, dd); 7.72(1H, s); 8.34-8.35(1H, d);16.3(1H, s). 4.24 4- H F H 1.98-2.06(2H, br m); 2.42-2.46(5H, s + t);2.70- methylphenyl 2.74(2H, t); 7.16-7.18(2H, d); 7.34-7.36(2H, d);7.65-7.69(1H, dd); 7.74(1H, s); 8.37-8.38(1H, d); 16.3(1H, s). 4.25 3- HF H 2.00-2.08(2H, m); 2.44-2.48(2H, br t); 2.72- chlorophenyl 2.76(2H,t); 7.20-7.22(1H, d); 7.32(1H, s); 7.44- 7.50(2H, m); 7.66-7.70(1H, dd);7.74(1H, s); 8.32-8.33(1H, d); 16.3(1H, s). 4.26 2,4- H F H 16.22 (1H,s), 8.34 (1H, d), 7.78 (1H, 1), 7.71 dichlorophenyl (1H, dd), 7.62 (1H,d), 7.44 (1H, dd), 7.32 (1H, d), 2.70-2.75 (2H, m), 2.36-2.53 (2H, m),2.09 (3H, s), 1.98-2.12 (2H, m) 4.27 2-methyl- H F H 8.30 (1H, d), 7.88(1H, t), 7.77 (1H, t), 7.68 pyridin-6-yl (1H, dd), 7.34 (1H, d), 7.24(1H, d), 2.72 (2H, bs), 2.65 (3H, s), 2.45 (2H, bs), 2.00-2.06 (2H, m)4.28 2- H F H 16.22 (1H, s), 8.34(1H, d), 7.78 (1H, 1), 7.68chlorophenyl (1H, dd), 7.56-4.62 (1H, m), 7.43-7.48 (2H, m), 7.36-7.40(1H, m), 2.68-2.74 (2H, m), 2.35- 2.45(2H, m), 2.09 (3H, s), 2.00-2.08(2H, m) 4.29 3,5- H F H 16.29(1H, s), 8.38(1H, d), 7.73(1H, s), 7.65(1H,dimethylphenyl dd), 7.10(1H, s), 6.90(2H, s), 2.71(2H, t), 2.45(2H, t),2.37(6H, s), 2.03(2H, t) 4.30 4- H F H 16.29(1H, s), 8.34(1H, d),7.74(1H, s), 7.68(1H, chlorophenyl dd), 7.52(2H, d), 7.25(2H, d),2.72(2H, t), 2.44(2H, br t), 2.03(2H, m) 4.31 4- H F H 16.33(1H, s),8.38(1H, d), 7.76(3H, m), 7.70 phenylphenyl (1H, dd), 7.64(2H, m),7.46(2H, t), 7.37(3H, m), 2.72(2H, t), 2.46(2H, br t), 2.03(2H, m) 4.323,4- H F H 16.28(1H, s), 8.34(1H, d), 7.73(1H, s), 7.68(1H,dichlorophenyl dd), 7.61(1H, d), 7.43(1H, d), 7.17(1H, m), 2.73(2H, t),2.45(2H, br t), 2.04(2H, m) 4.33 2- H F H 16.25(1H, s), 8.33(1H, d),7.78(1H, s), 7.67 methoxyphenyl (1H, dd), 7.47(1H, td), 7.27(dd),7.12(1H, td), 7.08(1H, dd) 4.34 2- H F H 8.30(1H, d), 7.86(1H, d),7.78(1H, s), 7.76 trifluoro- (1H, t), 7.68(1H, dd), 7.63(1H, t),7.39(1H, d), methylphenyl 2.65-2.76(2H, m), 2.33-2.53(2H, m), 2.09(3H,s), 1.96-2.10(2H, m). 4.35 2,4- H F H 16.25(1H, s), 8.34(1H, d),7.75(1H, s), 7.70 difluorophenyl (1H, dd), 7.38-7.30(1H, m),7.08-7.00(2H, m), 2.68-2.75(2H, m), 2.36-2.53(2H, m), 2.09(3H, s),1.98-2.10(2H, m) 4.36 2-nitrophenyl H F H 16.30(1H, s), 8.30-8.25(2H,m), 7.84-7.79(2H, m), 7.71-6.65(2H, m), 7.52(1H, dd), 2.70-2.75 (2H, m),2.33-2.53(2H, m), 2.09(3H, s), 1.96- 2.10(2H, m) 4.37 2,5- H F H16.10(1H, s), 8.36(1H, d), 7.83(1H, s), dimethylphenyl 7.72(1H, dd),7.30(1H, t), 7.21(1H, s), 2.71 (2H, t), 2.42(2H, t), 2.10(2H, quintet)

Biological Examples

Seeds of a variety of test species were sown in standard soil in pots(Alopecurus myosuroides (ALOMY), Setaria faberi (SETFA), Echinochloacrus-galli (ECHCG), Abuthilon theophrasti (ABUTH) and Amaranthusretoflexus (AMARE)). After cultivation for one day (pre-emergence) orafter 8 days cultivation (post-emergence) under controlled conditions ina glasshouse (at 24/16° C., day/night; 14 hours light; 65% humidity),the plants were sprayed with an aqueous spray solution derived from theformulation of the technical active ingredient in acetone / water(50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitanmonolaurate, CAS RN 9005-64-5). Compounds were applied at 250 g/ha. Thetest plants were then grown in a glasshouse under controlled conditionsin a glasshouse (at 24/16° C., day/night; 14 hours light; 65% humidity)and watered twice daily. After 13 days for pre and post-emergence, thetest was evaluated (100=total damage to plant; 0=no damage to plant).

POST Application PRE Application Compound ABUTH AMARE SETFA ALOMY ECHCGABUTH AMARE SETFA ALOMY ECHCG 1.2 80 80 80 40 80 70 40 70 20 90 1.19 8080 80 40 80 80 100 90 30 90 1.28 80 80 80 60 80 70 100 60 20 100 1.29 9090 90 30 80 90 100 10 30 100 1.42 50 70 60 0 70 0 0 0 0 0 1.43 80 80 8060 80 100 100 100 40 100 1.44 90 80 80 80 80 90 100 100 90 100 1.45 8080 80 60 80 100 100 80 70 100 1.46 100 70 70 70 80 80 100 80 60 100 1.4770 70 80 80 90 90 100 90 50 90 1.48 80 40 80 70 80 90 100 90 80 100 1.4980 70 70 70 80 90 100 90 60 100 1.50 80 70 80 70 80 90 90 100 80 1003.42 90 80 70 20 80 50 80 0 10 70 4.3 90 90 90 80 90 100 100 100 70 1004.4 90 80 90 90 90 100 100 100 90 100 4.9 80 80 80 90 80 100 100 100 90100 4.11 100 90 90 90 90 90 100 80 70 90 4.15 80 50 70 30 80 70 50 0 080 4.16 80 50 60 40 80 50 30 20 20 50 4.17 70 50 60 0 80 70 90 20 0 704.18 80 80 80 80 80 90 90 70 70 100 4.20 80 60 80 80 80 100 100 70 90100 4.22 80 70 80 80 70 90 100 100 90 100 4.23 80 80 70 70 80 80 70 9090 100 4.24 90 80 80 70 80 100 100 90 80 100 4.25 80 70 80 80 80 90 50100 90 100 4.28 80 80 80 70 80 100 50 100 90 100 4.33 80 80 90 100 90100 100 100 100 100 4.34 80 80 80 90 90 100 100 100 100 100 4.35 80 9080 90 90 100 100 100 90 100 4.36 80 80 80 90 90 100 100 100 90 100

1. A herbicidal compound of Formula (I):

or an agronomically acceptable salt of said compound, wherein: R¹ isselected from the group consisting of hydrogen, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₃alkoxy-C₁₋C₃ alkyl, C₁-C₃alkoxy-C₁-C₃alkoxy-C₁-C₃-alkyl, C₁-C₃alkoxy-C₁-C₃-haloalkyl,C₁-C₃-alkoxy-C₁-C₃-alkoxy-C₁-C₃-haloalkyl, C₄-C₆ -oxasubstitutedcycloalkoxy-C₁-C₃ -alkyl, C₄-C₆-oxasubstitutedcycloalkyl-C₁-C₃-alkoxy-C₁-C₃-alkyl, C₄-C₆-oxasubstitutedcycloalkoxy-C₁-C₃ -haloalkyl, C₄-C₆-oxasubstitutedcycloalkyl-C₁-C₃-alkoxy-C₁-C₃-haloalkyl, (C₁-C₃ alkanesulfonyl-C₁-C₃alkylamino)-C₁-C₃ alkyl, (C₁-C₃ alkanesulfonyl-C₃-C₄cycloalkylamino)-C₁-C₃alkyl, C₁-C₆alkylcarbonyl-C₁-C₃alkyl,C₃-C₆cycloalkyl-C₂-C₆alkenyl, C₃-C₆alkynyl, C₂-C₆-alkenyl,C₂-C₆-haloalkenyl, cyano-C₁-C₆alkyl, arylcarbonyl-C₁-C₃alkyl,aryloxycarbonyl-C₁-C₃alkyl (wherein in both cases the aryl may beoptionally substituted with one or more substituents from the groupconsisting of halo, C₁-C₃alkoxy, C₁-C₃alkyl, C₁-C₃haloalkyl),aryl-C₁-C₆alkyl (wherein the aryl may be optionally substituted with oneor more substituents from the group consisting of halo, C₁-C₃-alkoxy,C₁-C₃-alkyl, C₁-C₃ haloalkyl) and a three- to ten-membered mono- orbicyclic ring system, which may be aromatic, saturated or partiallysaturated and can contain from 1 to 4 heteroatoms each independentlyselected from the group consisting of nitrogen, oxygen and sulphur thering system being optionally substituted by one or more substituentsselected from the group consisting of C₁-C₃alkyl, C₁-C₃haloalkyl,C₁-C₃alkenyl, C₁-C₃alkynyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy,C₁-C₆alkyl-S(O)p-, C₁-C₆haloalkyl-S(O)p-, aryl, aryl-S(O)p,heteroaryl-S(O)p, aryloxy, heteroaryloxy, C₁-C₃ alkoxycarbonyl, C₁-C₃alkylamino-S(O)p-, C₁-C₃ alkylamino-S(O)p-C₁-C₃ alkyl, C₁-C₃dialkylamino-S(O)p-, C₁-C₃ dialkylamino-S(O)p-C₁-C₃ alkyl, C₁-C₃alkylaminocarbonyl-, C₁-C₃ alkylaminocarbonyl-C₁-C₃ alkyl, C₁-C₃dialkylaminocarbonyl, C₁-C₃ dialkylaminocarbonyl-C₁-C₃ alkyl, C₁-C₃alkylcarbonylamino, C₁-C₃ alkyl-S(O)p-amino, cyano and nitro; theheteroaryl substituents containing one to three heteroatoms eachindependently selected from the group consisting of oxygen, nitrogen andsulphur, and wherein the aryl or heteroaryl component may be optionallysubstituted by one or more substituents selected from the groupconsisting of halo, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃ alkoxy, C₁-C₃haloalkoxy, phenyl, cyano and nitro; R⁵ is selected from the groupconsisting of hydrogen, chloro, fluoro and methyl; R⁶ is selected fromthe group consisting of hydrogen, fluorine, chlorine, hydroxyl andmethyl; R⁷ is selected from the group consisting of hydrogen, cyano,nitro, halogen, hydroxyl, sulfhydryl, C₁-C₆alkyl, C₃-C₆cycloalkyl,C₁-C₆haloalkyl, C₂-C₆haloalkenyl, C₂-C₆alkenyl, aryl-C₂-C₆alkenyl,C₃-C₆alkynyl, C₁-C₆alkoxy, C₄-C₇cycloalkoxy, C₁-C₆haloalkoxy,C₁-C₆alkyl-S(O)p, C₃-₆cycloalkyl-S(O)p C₁-C₆haloalkyl-S(O)p, C₃-C₆halocycloalkyl-S(O)p, C₁-C₆alkylcarbonylamino,(C₁-C₆alkylcarbonyl)C₁-C₃alkylamino, (C₃-C₆cycloalkylcarbonyl)amino,(C₃-C₆cycloalkylcarbonyl)C₁-C₃alkylamino, arylcarbonylamino,(arylcarbonyl)-C₁-₃alkylamino, (heteroarylcarbonyl)amino,(heteroarylcarbonyl)C₁-C₃alkylamino, amino,C₁-C₆alkylamino,C₂-C₆dialkylamino, C₂-C₆alkenylamino, C₁-C₆alkoxy-C₂-C₆-alkylamino,(C₁-C₆alkoxy-C₂-C₄-alkyl)-C₁-C₆-alkylamino, C₃-C₆ cycloalkylamino, C₃-C₆cyclohaloalkylamino, C₁-C₃alkoxy-C₃-C₆ cycloalkylamino, C₃-C₆alkynylamino, dialkylamino in which the substituents join to form a 4-6membered ring optionally containing oxygen and/or optionally substitutedby C₁-C₃-alkoxy and/or halogen (especially fluorine),C₂-C₆dialkylaminosulfonyl, C₁-C₆alkylaminosulfonyl,C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkoxy-C₂-C₆alkoxy, C₁-C₆alkoxy-C₂-C₆alkoxy-C₁-C₆-alkyl, C₃-C₆alkenyl-C₂-C₆alkoxy, C₃-C₆alkynyl-C₁-C₆alkoxy,C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₄alkylenyl-S(O)p-R′,C₁-C₄alkylenyl-CO₂-R′, C₁-C₄alkylenyl-(CO)N—R′R′, aryl, aryl-C₁-C₃alkyl,aryl-S(O)p, heteroaryl-S(O)p, aryloxy, a 5 or 6-membered heteroaryl,heteroaryl C₁-C₃ alkyl and heteroaryloxy, the heteroaryl containing oneto three heteroatoms, each independently selected from the groupconsisting of oxygen, nitrogen and sulphur, wherein the aryl orheteroaryl component may be optionally substituted by one or moresubstituents selected from the group consisting of C₁-C₃alkyl,C₁-C₃haloalkyl, C₁-C₃ alkoxy, C₁-C₃haloalkoxy, halo, cyano and nitro;X¹═N—(O)n or C—R⁸; X²=O or S; n=0 or 1; p=0, 1 or 2; R′ is independentlyselected from the group consisting of hydrogen and C₁-C₆alkyl; R⁸ isselected from the group consisting of hydrogen, halogen, C₁-C₆alkyl,C₁-C₆haloalkyl, C₁-C₆alkylcarbonyl-C₁-C₃alkyl,C₃-C₆cycloalkyl-C₂-C₆alkenyl for example cyclohexylmethylenyl,C₃-C₆alkynyl, C₂-C₆-alkenyl, C₁-C₆alkoxy C₁-C₆alkyl, cyano-C₁-C₆-alkyl,arylcarbonyl-C₁-C₃-alkyl (wherein the aryl may be optionally substitutedwith one or more substituents selected from the group consisting ofhalo, C₁-C₃-alkoxy, C₁-C₃-alkyl, C₁-C₃ haloalkyl), aryl-C₁-C₆alkyl(wherein the aryl may be optionally substituted with one or moresubstituents from the group consisting of halo, C₁-C₃-alkoxy,C₁-C₃-alkyl, C₁-C₃ haloalkyl), C₁-C₆alkoxy C₁-C₆alkoxy C₁-C₆alkyl, aryl,5 or 6-membered heteroaryl, a 5 or 6-membered heteroaryl-C₁-C₃-alkyl andheterocyclyl-C₁-C₃-alkyl, the heteroaryl or heterocyclyl containing oneto three heteroatoms each independently selected from the groupconsisting of oxygen, nitrogen and sulphur, and wherein the aryl,heterocyclyl or heteroaryl component may be optionally substituted byone or more substituents from the group consisting of halogen,C₁-C₃alkyl, C₁-C₃haloalkyl and C₁-C₃ alkoxy, cyano and nitro; Q isselected from the group consisting of:

wherein A¹ is selected from the group consisting of O, C(O), S, SO, SO₂and (CR^(a)R^(f))_(q); q=0, 1 or 2; R^(a), R^(b), R^(c), R^(d), R^(e)and R^(f) are each independently selected from the group consisting ofC₁-C₄alkyl which may be mono-, di- or tri-substituted by substituentsselected from the group consisting of C₁-C₄alkoxy, halogen, hydroxy,cyano, hydroxycarbonyl, C₁-C₄alkoxycarbonyl, C₁-C₄alkylthio,C₁-C₄alkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄alkyl-carbonyl, phenyl andheteroaryl, it being possible for the phenyl and heteroaryl groups inturn to be mono-, di- or tri-substituted by substituents selected fromthe group consisting of C₁-C₄alkoxy, halogen, hydroxy, cyano,hydroxycarbonyl, C₁-C₄alkoxycarbonyl, C₁-C₄alkylsulfonyl andC₁-C₄haloalkyl, the substituents on the nitrogen in the heterocyclicring being other than halogen; or R^(a), R^(b), R^(c), R^(d), R^(e) andR^(f) are each independently selected from the group consisting ofhydrogen, C₁-C₄alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl,C₁-C₄alkoxycarbonyl, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl,C₁-C₄alkylsulfonyl, C₁-C₄alkylcarbonyl, phenyl or heteroaryl, it beingpossible for the phenyl and heteroaryl groups in turn to be mono-, di-or tri-substituted by substituents selected from the group consisting ofC₁-C₄alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl,C₁-C₄alkoxycarbonyl, C₁-C₄alkylsulfonyl and C₁-C₄haloalkyl, thesubstituents on the nitrogen in the heterocyclic ring being other thanhalogen; or R^(a) and R^(b) together form a 3- to 5-membered carbocyclicring which may be substituted by C₁-C₄alkyl and may be interrupted byoxygen, sulfur, S(O), SO₂, OC(O), NR^(g) or by C(O); or R^(a) and R^(c)together form a C₁-C₃alkylene chain which may be interrupted by oxygen,sulfur, SO, SO₂, OC(O), NR^(h) or by C(O); it being possible for thatC₁-C₃alkylene chain in turn to be substituted by C₁-C₄alkyl; R^(g) andR^(h) are each independently of the other C₁-C₄alkyl, C₁-C₄haloalkyl,C₄alkylsulfonyl, C₁-C₄alkylcarbonyl or C₁-C₄alkoxycarbonyl; R^(i) isC₁-C₄alkyl; R^(j) is selected from the group consisting of hydrogen,C₁-C₄ alkyl and C₃-C₆ cycloalkyl; R³ is selected from the groupconsisting of C₁-C₆alkyl, optionally substituted with halogen and/orC₁-C₃alkoxy, and C₃-C₆ cycloalkyl optionally substituted with halogenand/or C₁-C₃alkoxy; R⁹ is selected from the group consisting ofcyclopropyl, CF₃ and i.-Pr; R¹⁰ is selected from the group consisting ofhydrogen, I, Br, SR¹¹, S(O)R¹¹, S(O)₂R¹¹ and CO₂R¹¹; and R¹¹ is C₁₋₄alkyl.
 2. A herbicidal compound according to claim 1, wherein the three-to ten-membered mono- or bicyclic ring system of R¹ is selected from thegroup consisting of aryl, a 5 or 6-membered heteroaryl, a 5 or6-membered heteroaryl-C₁-C₃alkyl and heterocyclyl-C₁-C₃alkyl, theheteroaryl or heterocyclyl containing one to three heteroatoms eachindependently selected from the group consisting of oxygen, nitrogen andsulphur, and wherein the aryl, heterocyclyl or heteroaryl component maybe optionally substituted by one or more substituents selected from thegroup consisting of halo, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃ alkoxy,cyano and nitro.
 3. A herbicidal compound according to claim 1 havingFormula (Ia)

wherein R⁷ is selected from the group consisting of hydrogen, hydroxyl,halogen, C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy,C₁-C₆ alkoxy-C₂-C₆-alkoxy, C₁-C₆-alkoxy-C₁-C₆ alkyl,C₁-C₆-alkoxy-C₂-C₆-alkoxy-C₁-C₆ alkyl, C₁-C₆alkylamino,C₁-C₆dialkylamino, C₂-C₆alkenylamino, C₁-C₆alkoxy-C₂-C₃-alkylamino,(C₁-C₆alkoxy-C₂-C₄-alkyl)-C₁-C₆-alkylamino, C₃-C₆ cycloalkylamino, C₃-C₆cyclohaloalkylamino, C₁-C₃alkoxy-C₃-C₆ cycloalkylamino, C₃-C₆alkynylamino and dialkylamino group in which the substituents join toform a 4-6 membered ring, optionally containing oxygen, and/oroptionally substituted by C₁-C₃-alkoxy and/or halogen.
 4. A herbicidalcompound according to claim 3, wherein R⁷ is selected from the groupconsisting of hydrogen, chloro, methyl, ethyl, 1-methylethyl,cyclopropyl, fluoromethyl, 1-fluoroethyl, 1,1-difluoroethyl,2,2-difluoroethyl, 1-fluoro-1-methylethyl, 2,2,2-trifluoroethyl,difluorochloromethyl, methoxy, ethoxy, methoxymethyl, 1-methoxyethyl,2-methoxyethoxy, 2-methoxyethoxymethyl, (2-methoxyethyl)amino and(2-methoxyethyl) methylamino.
 5. A herbicidal compound according toclaim 1 having Formula (Ib)

wherein R⁷ is selected from the group consisting of hydrogen, cyano,halogen, nitro, C₁-C₆ haloalkyl, C₁-C₃ alkoxyC₁-C₃ haloalkyl, C₁-C₃alkoxyC₂-C₆-alkoxyC₁-C₃ haloalkyl, C₁-C₆haloalkoxy, C₁-C₆alkylS(O)p,C₃-₆cycloalkylS(O)p C₁-C₆haloalkyl-S(O)p, C₃-C₆halocycloalkyl-S(O)p,aryl-S(O)p and heteroaryl-S(O)p.
 6. A herbicidal compound according toclaim 5, wherein R⁷ is selected from the group consisting of chloro,fluoro, cyano, nitro, fluoromethyl, difluoromethyl, trifluoromethyl,1-fluoroethyl, 1,1-difluoroethyl, 1-fluoro-1-methylethyl,difluorochloromethyl, difluoromethoxy, trifluoromethoxy,1,1-difluoroethoxy, methylsulfinyl, methylsulfonyl, ethylsulfinyl,ethylsulfonyl, phenyl sulfinyl and phenyl sulfonyl
 7. A herbicidalcompound according to claim 1, wherein Q is Q1.
 8. A herbicidal compoundaccording to claim 7, wherein A¹ is CR^(e)R^(f) and wherein R^(a),R^(b), R^(c), R^(d), R^(e) and R^(f) are hydrogen and wherein q=1.
 9. Aherbicidal compound of claim 1, wherein R¹ is selected from the groupconsisting of hydrogen, C₁-C₆alkyl, C₁-C₃alkoxyC₁-C₃alkyl, C₁-C₃alkoxyC₂-C₃alkoxyC₁-C₃alkyl, C₁-C₆haloalkyl, C₁-C₃alkoxy-C₁₋C₃haloalkyl, aryl(especially phenyl) and a 5 or 6-membered heteroaryl containing one tothree heteroatoms each independently selected from the group consistingof oxygen, nitrogen and sulphur, and wherein the aryl or heteroaryl maybe optionally substituted by one or more substituents selected from thegroup consisting of halo, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃ alkoxy,C₁-C₃ haloalkoxy, C₁-C₆alkyl-S(O)p-, C₁-C₆haloalkyl-S(O)p-, cyano andnitro.
 10. A herbicidal compound according to claim 9, wherein R¹ isselected from the group consisting of methyl, propyl, iso-butyl,methoxymethyl, methoxyethyl, 2,2 difluoroethyl, 1,1-difluoro-but-1-enyl,1-propenyl, thiophenyl, benzyl, phenyl and phenoxy.
 11. A herbicidalcompound according to claim 1, wherein R⁶ is hydrogen or fluorine. 12.An agronomically acceptable salt of the compound according claim 1,wherein the salt is selected from the group consisting of Na⁺, Mg²⁺ andCa²⁺.
 13. A herbicidal composition comprising a herbicidal compoundaccording to claim 1 and an agriculturally acceptable formulationadjuvant.
 14. A herbicidal composition according to claim 13, furthercomprising at least one additional pesticide.
 15. A herbicidalcomposition according to claim 14, wherein the additional pesticide is aherbicide or herbicide safener.
 16. A method of selectively controllingweeds at a locus comprising crop plants and weeds, wherein the methodcomprises application to the locus of a weed controlling amount of acomposition according to claim
 1. 17. A method of making a compound ofFormula (I) wherein Q=Q1 which comprises reacting together a compound ofFormula (Ia′)

wherein the various substituents are as defined in claim 1, and whereinR¹² is halogen or aryloxy with a compound of Formula (II)

wherein the various substituents are as defined in claim 1, in thepresence of an inert organic solvent and a base.
 18. A compound ofFormula (III)

wherein R¹, R⁵, R⁶, R⁷, X¹, X² are as defined in claim 1 above; and R¹³is selected from the group consisting of halogen, C₁-C₆-alkoxy, OH,O⁻M⁺wherein M⁺ is an alkali metal cation or an ammonium cation with theexception of 1,6,7-Trimethyl-2-oxo-1,2-dihydro-quinoline-3-carboxylicacid, 1 ,6,7-Trimethyl-2-oxo-1 ,2-dihydro-quinoline-3-carboxylic acidmethyl ester,1,2-dihydro-2-oxo-1-[3-(trifluoromethyl)phenyl-1,8-naphthyridine-3-carboxylicacid and1,2-dihydro-2-oxo-1-[3-(trifluoromethyl)phenyl-1,8-naphthyridine-3-carboxylicacid ethyl ester.
 19. (Deleted)